Polyphenylene ether oligomer compound, derivatives thereof and use thereof

ABSTRACT

The present invention provides a bifunctional phenylene ether oligomer compound having a thermosetting functional group at each terminal, an epoxy resin containing the above oligomer compound and a use thereof. That is, it provides a sealing epoxy resin composition for sealing an electric part, an epoxy resin composition for laminates, a laminate, a printed wiring board, a curable resin composition and a photosensitive resin composition. The resins and resin compositions of the present invention are used in electronics fields in which a low dielectric constant, a low dielectric loss tangent and high toughness are required and also used for various uses such as coating, bonding and molding.

FIELD OF THE INVENTION

The present invention relates to a bifunctional phenylene ether oligomercompound having a thermosetting functional group at each terminal, anepoxy resin containing the above oligomer compound and a use thereof.More specifically, it relates to a sealing epoxy resin composition forsealing an electric part, an epoxy resin composition for laminates, alaminate, a printed wiring board, a curable resin composition and aphotosensitive resin composition. The resins and resin compositions ofthe present invention are used in electronics fields in which a lowdielectric constant, a low dielectric loss tangent and high toughnessare required and also used for various uses such as coating, bonding andmolding.

BACKGROUND OF THE INVENTION

As for materials for use in an electric or electronic field, as thespeed of transmission signal increases, a low dielectric constant whichdecreases a time delay and a low dielectric loss tangent which decreasesa loss are desired for utilizing a high-frequency wave (gigahertz band).Further, higher toughness is also desired in order to inhibit theoccurrence of microcracks which are thought to be generated by thermalshock and secure high reliability. For the above demands, there arecarried out attempts of incorporation of engineering plastic, such aspolyphenylene ether (PPE), as a modified polymer having severalproperties. However, since a thermoplastic resin is directlyincorporated into a thermosetting resin, problems remain with regard tothe compatibility between the resins and molding processability.

For improving the compatibility, a method of improving compatibility byblending PPE with a different resin as a compatibilizing agent isdiscussed and the pseudo IPN structuralization of PPE and a cyanateresin is also discussed (JP-A-11-21452, etc.). However, the problems ofmolding processability and heat resistance have not been solved yet.Further, a method of converting a high molecular PPE into a lowmolecular compound is discussed for improving moldability. For example,there is known a method in which a high molecular PPE and polyphenolsare redistributed in the presence of a radical catalyst (JP-A-9-291148,etc.). Further, for obtaining toughness, there is known a method inwhich a bivalent phenol and a monovalent phenol are subjected tooxidation polymerization to obtain a thermosetting resin having acyanate ester group (JP-B-8-011747).

Concerning a semiconductor device, an epoxy resin composition isgenerally used for sealing electronic parts such as a semiconductor. Theabove-mentioned epoxy resin composition is composed of various epoxyresins such as a cresol novolak type epoxy resin, a bisphenol A typeepoxy resin and a biphenyl type epoxy resin, a curing agent therefor, aninorganic filler, a curing accelerator as required, a coupling agent, areleasing agent, a coloring agent and the like.

In compliance with recent requirements for a decrease in size or adecrease in thickness, the formation technique of the above electronicparts is being changed from a conventional through hole mounting method(DIP: dual inline package, etc.) to a surface mounting method (SOP:small outline package, QFP: quad flat package, etc.). In the surfacemounting method, since a semiconductor device is treated at a hightemperature (for example 210° C.˜260° C.) at a solder reflow or the likeat a mounting time, a high temperature heat is applied to the entiresemiconductor device. In this case, problems such as the occurrence ofcracks in a sealing layer formed of the above epoxy resin compositionand a large decrease in humidity resistance are apt to occur.

Countermeasures against the above are proposed. One countermeasure withrespect to handling is that a semiconductor device before mounting ispackaged in a moisture-proof case. As an improvement in a sealing epoxyresin composition, for example, JP-A-1-108256 discloses a sealingmaterial containing a biphenyl type epoxy resin andJP-A-64-24825discloses a sealing material containing an epoxy resin anda polyphenylene ether type resin in combination.

However, these sealing materials have problems. For example, when a thinsealing layer having a thickness of 2.0 mm or less is used, cracks areapt to occur at the time of a solder reflow. In view of a furtherimprovement in physical properties and an increase in a signaltransmission speed in a chip circuit, it is demanded to carry out asealing with a sealing layer having a lower dielectric constant.

With the advance of communication or computers, recently, higherfrequency waves come to be used. Printed wiring boards are required tohave low dielectric characteristics for the purpose of increasing asignal transmittal speed. For responding to the above demands, there areused thermoplastic resins such as a fluororesin excellent in dielectriccharacteristics or a general polyphenylene ether. However, thesethermoplastic resins have problems about workability, moldability, heatresistance and the like. For example, the problems are that a solventused for preparing a varnish is limited, and that due to a high meltviscosity, a high multilayer formation can not be carried out and a hightemperature and a high pressure are required at a molding time

On the other hand, as a thermosetting resin, there are known apolyphenylene ether modified epoxy resin, a thermosetting typepolyphenylene ether and the like. However, conventional thermosettingresins have the same problems as the above problems of the thermoplasticresins. Further, a cyanate ester resin is known as a thermosetting resinhaving excellent dielectric characteristic and excellent moldability.However, when a cyanate ester resin alone is used, a cured product istoo hard and is fragile so that it has a problem about adhesive propertyand solder resistance. When a cyanate ester resin is used in combinationwith an epoxy resin, the above defects can be covered. However, it isdifficult to cope with requirements of lower dielectric characteristicsof laminates, which requirements are becoming severer, by using aconventional cyanate ester resin in combination with a conventionalepoxy resin.

Epoxy(meth)acrylate compounds have been widely used as raw materials forvarious functional high molecular materials such as a photosensitivematerial, an optical material, a dental material, an electronic materialand crosslinking agents for various polymers. However, since higherperformances are required in these application fields in recent years,physical properties required as a functional high molecular materialbecome severer increasingly. As such physical properties, for example,heat resistance, weather resistance, low moisture absorptivity, highrefractive index, high fracture toughness, low dielectric constant andlow dielectric loss tangent are required. Until now, these requiredphysical properties have not been necessarily satisfied.

For example, concerning the production of a printed wiring board, it isknown that epoxy(meth)acrylate compounds are used for a photo solderresist used as a permanent mask. As a resist material like above, thereare known a novolak type epoxy acrylate compound disclosed inJP-A-61-243869, a bisphenol fluorene type epoxy acrylate compounddisclosed in JP-A-3-205417 and acid-modified products of these epoxyacrylate compounds. In a use for a printed wiring board, heat resistancein an immersion into a solder bath is demanded. When the heat resistanceis insufficient, swelling or peeling off of a resist film occurs, whichcauses defectives.

In addition to the above-mentioned heat resistance, recently, as thespeed of transmission signal becomes high, a lower dielectric constantwhich decreases a time delay and a lower dielectric loss tangent whichdecreases a loss are desired for utilizing a high-frequency wave(gigahertz band) However, a conventional epoxy(meth)acrylate compound isinsufficient in dielectric characteristics for coping with ahigh-frequency wave. For this reason, a novel epoxy (meth)acrylatecompound which satisfies the above requirements is demanded.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a thermosettingresin having the excellent electric characteristics and toughness ofpolyphenylene ether (to be referred to as “PPE” hereinafter) andimproved in compatibility with a different resin and moldingprocessability.

It is another object of the present invention to provide molded articleswhich can be widely used in various uses including a use in anelectronics field.

It is further another object of the present invention to provide asealing epoxy resin composition capable of giving a sealing layer whichis free from the occurrence of cracks when it is exposed to a hightemperature, such as a temperature in a solder reflow, and has a lowdielectric constant.

It is further another object of the present invention to provide athermosetting resin composition excellent in dielectric characteristicsand also excellent in moldability, heat resistance and the like, alaminate using the thermosetting resin composition and a printed wiringboard.

It is further another object of the present invention to provide a novel(meth)acrylate compound and a curable resin composition which haveexcellent heat resistance and have a low dielectric constant and a lowdielectric loss tangent.

According to the present invention 1, there is provided a thermosettingresin represented by the formula (1),

-   -   wherein —(O—X—O)— is represented by the formula (2) in which R₁,        R₂, R₇ and R₈ may be the same or different and are a halogen        atom, an alkyl group having 6 or less carbon atoms or a phenyl        group, R₃, R₄, R₅ and R₆ may be the same or different and are a        hydrogen atom, a halogen atom, an alkyl group having 6 or less        carbon atoms or a phenyl group and A is a linear, branched or        cyclic hydrocarbon having 20 or less carbon atoms or an aromatic        group, —(Y—O)— is represented by the formula (3) in which R₉ and        R₁₀ may be the same or different and are a halogen atom, an        alkyl group having 6 or less carbon atoms or a phenyl group and        R₁₁ and R₁₂ may be the same or different and are a hydrogen        atom, a halogen atom, an alkyl group having 6 or less carbon        atoms or a phenyl group, —(Y—O)— is an arrangement of one kind        of structure defined by the formula (3) or a random arrangement        of two or more kinds of structures defined by the formula (3), Z        is an organic group which has one or more carbon atoms and may        contain an oxygen atom, each of a and b is 0 or an integer of 1        to 300, provided that at least either a or b is not 0, and each        of i is independently 0 or an integer of 1.

According to the present invention 2, there is provided a sealing epoxyresin composition containing as ingredients an epoxy resin, a curingagent, an inorganic filler and a polyphenylene ether oligomer compoundhaving a number average molecular weight of 700 to 3,000 and having anepoxy group at each terminal, represented by the formula (9),

-   -   wherein —(O—X—O)—, —(Y—O)—, Z, A and i are as defined in the        formula (1), each of a and b is 0 or an integer of 1 to 20,        provided that at least either a or b is not 0, each of c and d        is 0 or an integer of 1 to 20, provided that at least either c        or d is not 0, and j is 0 or an integer of 1 to 5.

According to the present invention 3, there are provided an epoxy resincomposition for laminates, containing a polyphenylene ether oligomerepoxy compound having a number average molecular weight of 700 to 3,000and having an epoxy group at each terminal, represented by the aboveformula (9), and a curing agent as ingredients, prepreg and a printedwiring board.

According to the present invention 4, there are provided a(meth)acrylate compound represented by the following formula (10), acurable resin composition containing the (meth)acrylate compound and acured product obtained by curing the curable resin composition,

-   -   wherein R₁ is a hydrogen atom or a methyl group, —(O—X—O)— is        represented by the formula (11) in which R₂, R₃, R₈ and R₉ may        be the same or different and are a halogen atom, an alkyl group        having 6 or less carbon atoms or a phenyl group, R₄, R₅, R₆ and        R₇ may be the same or different and are a hydrogen atom, a        halogen atom, an alkyl group having 6 or less carbon atoms or a        phenyl group and A is a linear, branched or cyclic hydrocarbon        having 20 or less carbon atoms, —(Y—O)— is an arrangement of one        kind of structure defined by the formula (12) or a random        arrangement of two or more kinds of structures defined by the        formula (12) in which R₁₀ and R₁₁ may be the same or different        and are a halogen atom, an alkyl group having 6 or less carbon        atoms or a phenyl group and R₁₂ and R₁₃ may be the same or        different and are a hydrogen atom, a halogen atom, an alkyl        group having 6 or less carbon atoms or a phenyl group, Z is an        organic group which has no OH group in a side chain and has one        or more carbon atoms and which may contain an oxygen atom, each        of a and b is 0 or an integer of 1 to 300, provided that at        least either a or b is not 0, and each of c and d is 0 or an        integer of 1.

According to the present invention 5, there are provided anepoxy(meth)acrylate compound represented by the formula (16), a curableresin composition containing the above compound and a cured product ofthe above resin composition,

-   -   wherein R₁, —(O—X—O)—, A, —(Y—O)—, a, b, c and d are as defined        in the formula (10), Z is an organic group which has one or more        carbon atoms and may contain an oxygen atom, and n is 0 or an        integer of 1 to 10.

According to the present invention 5, further, there is provided anepoxy(meth)acrylate compound according to the above, wherein R₂, R₃, R₈and R₉ in —(O—X—O)— are a methyl group, and —(Y—O)— has an arrangementstructure of the formula (4) or the formula (5) or a random arrangementstructure of the formula (4) and the formula (5).

According to the present invention 6, there is provided a thermosettingresin represented by the formula (17), a resin composition for laminatescontaining the above thermosetting resin, prepreg obtained by using theresin composition and a printed wiring board,

-   -   wherein —X— is represented by the formula (18) in which R₁, R₂,        R₇ and R₈ may be the same or different and are a halogen atom,        an alkyl group having 6 or less carbon atoms or a phenyl group,        R₃, R₄, R₅ and R₆ may be the same or different and are a        hydrogen atom, a halogen atom, an alkyl group having 6 or less        carbon atoms or a phenyl group and A is a cyclic hydrocarbon or        an organic group having an aromatic group, —(O—Y)— is        represented by the formula (19) in which R₉ and R₁₀ may be the        same or different and are a halogen atom, an alkyl group having        6 or less carbon atoms or a phenyl group and R₁₁ and R₁₂ may be        the same or different and are a hydrogen atom, a halogen atom,        an alkyl group having 6 or less carbon atoms or a phenyl group,        —(O—Y)— is an arrangement of one kind of structure defined by        the formula (19) or a random arrangement of two or more kinds of        structures defined by the formula (19), Z is an organic group        which has one or more carbon atoms and may contain an oxygen        atom, each of a and b is an integer of 0 to 300, provided that        at least either a or b is not 0, and each of i is independently        an integer of 0 or 1).

DETAILED DESCRIPTION OF THE INVENTION

The present inventors have made diligent studies concerning athermosetting resin having the excellent toughness of PPE and furtherhaving low dielectric characteristics and, as a result, found that theabove purposes are satisfied by an epoxy resin which is obtained bydehydrohalogenation of a bifunctional PPE of the formula (6), obtainedby oxidation copolymerization between a bivalent phenol and a monovelentphenol, and a halogenated glycidyl such as epichlorohydrin in thepresence of a base, and an allyl resin which is obtained bydehydrohalogenation of a bifunctional PPE of the formula (6) and anallyl halide such as allyl bromide in the presence of a phase transfercatalyst under a base condition. On the basis of the above finding, thepresent inventors have completed the present invention 1. The presentinvention 1 will be explained in detail hereinafter.

The present invention 1 is characterized in that, concerning oxidationpolymerization of phenols, a bivalent phenol and a monovelent phenol arecopolymerized to efficiently synthesize a bifunctional PPE and then thesynthesized PPE is converted into a thermosetting resin (epoxy compound,allyl compound) having a higher activity which is to be incorporatedinto a network in a resin constitution. Here, as the bivalent phenol tobe used as raw materials, there are used bisphenols in which at least 2-and 6-positions are substituted. Further, as the monovalent phenol usedas raw materials, there are used monovalent phenols having substituentsat 2- and 6-positions which are required for the oxidationpolymerization and compounds in which a substituent is furtherintroduced at 3-position. Thus, the present invention is completed. Aresin having the excellent electric characteristics of PPE has beendeveloped by an influence of a phenylene ether structure and aninfluence of an increase in the number of methyl groups due to thecopolymerization of these. That is, the present inventors have foundthat a bifunctional type PPE is very important to the present invention1.

The bifunctional PPE oligomer compound, which is an intermediate productof the present invention 1, has a structure represented by the followingformula (6) in which —(O—X—O)— is represented by the formula (2) and—(Y—O)— is an arrangement of one kind of structure defined by theformula (3) or a random arrangement of two or more structures defined bythe formula (3). In the formulae, R₁, R₂, R₇, R₈, R₉ and R₁₀ may be thesame or different and are a halogen atom, an alkyl group having 6 orless carbon atoms or a phenyl group, R₃, R₄, R₅, R₆, R₁₁ and R₁₂ maybethe same or different and are a hydrogen atom, a halogen atom, an alkylgroup having 6 or less carbon atoms or a phenyl group, A is a linear,branched or cyclic hydrocarbon having 20 or less carbon atoms, each of aand b is 0 or an integer of 1 to 300, provided that at least either a orb is not 0. The bifunctional PPE oligomer compound is a PPE oligomercompound in which it is essential that R₁, R₂, R₇, R₈, R₉ and R₁₀ arenot a hydrogen atom.

The bifunctional PPE oligomer compound which is an intermediate productof the present invention 1 will be explained. The PPE oligomer compoundrepresented by the formula (6) is effectively produced by oxidativelypolymerizing a bivalent phenol represented by the formula (7) with amonovalent phenol defined by the formula (8) or a mixture of monovalentphenols defined by the formula (8) in a toluene-alcohol solvent, atoluene-ketone solvent or a ketone solvent.

Here, the bivalent phenol of the formula (7) is a bivalent phenol inwhich R₁, R₂, R₇ and R₈ may be the same or different and are a halogenatom, an alkyl group having 6 or less carbon atoms or a phenyl group,R₃, R₄, R₅ and R₆ may be the same or different and are a hydrogen atom,a halogen atom, an alkyl group having 6 or less carbon atoms or a phenylgroup and A is a linear, branched or cyclic hydrocarbon having 20 orless carbon atoms or an aromatic group, provided that it is essentialthat R₁, R₂, R₇ and R₈ are not a hydrogen atom. Examples of the bivalentphenol will be shown hereinafter.

-   -   4,4′-methylenebis(2,6-dimethylphenol),    -   4,4′-(1-methylethylidene)bis[2,6-dimethylphenol],    -   4,4′-methylenebis(2,3,6-trimethylphenol),    -   4,4′-cyclohexylidenebis[2,6-dimethylphenol),    -   4,4′-(phenylmethylene)bis-2,3,6-trimethylphenol,    -   4,4′-[1,4-phenylenebis(1-methylethylidene)bis[2,6-dimethyl        phenol],    -   4,4′-methylenebis[2,6-bis(1,1-dimethylethyl)phenol],    -   4,4′-cyclopentylidenebis[2,6-dimethylphenol],    -   4,4′-[2-furylmethylene]bis(2,6-dimethylphenol),    -   4,4′-[1,4-phenylenebismethylene]bis[2,6-dimethylphenol],    -   4,4′-(3,3,5-trimethylcyclohexylidene)bis[2,6-dimethylphenol],    -   4,4′-[4-(1-methylethyl)cyclohexylidene)bis[2,6-dimethylphenol],    -   4,4′-(4-methylphenylethylene)bis[2,3,6-trimethylphenol],    -   4,4′-[1,4-phenylenebismethylene]bis[2,3,6-trimethylphenol],    -   4-[1-[4-(4-hydroxy-3,5-dimethylphenyl)-4-methylcyclohexyl]-1-methylethyl]-2,6-dimethylphenol,    -   4,4′-(4-methoxyphenylmethylene)bis[2,3,6-trimethylphenol],    -   4,4,-[4-(1-methylethyl)phenylmethylene]bis[2,3,6-trimethyl        phenol],    -   4,4′-(9H-fluorene-9-ylidene)bis[2,6-dimethylphenol],    -   4,4′-[1,3-phenylelebis(1-methylethylidene)]bis[2,3,6-trimethylphenol],    -   4,4′-(1-2-ethanediyl)bis[2,6-di-(1,1-dimethylethyl)phenol]and    -   5,5′-(1-methylethylidene)bis[3-(1,1-dimethylethyl)-1,1-biphenyl-2-ol].

In the monovalent phenol of the formula (8), R₉ and R₁₀ may be the sameor different and are a halogen atom, an alkyl group having 6 or lesscarbon atoms or a phenyl group and R₁₁ and R₁₂ may be the same ordifferent and are a hydrogen atom, a halogen atom, an alkyl group having6 or less carbon atoms or a phenyl group. In particular, it is preferredthat a monovalent phenol having substituents at the 2-and 6-positions isused alone or used in combination with a monovalent phenol havingsubstituent(s) at the 3-position or at the 3- and 5-positions inaddition to the 2- and 6-positions. More preferably, when used alone,2,6,-dimethylphenol or 2,3,6-trimethylphenol is preferred, and when usedin combination, 2,6,-dimethylphenol and 2,3,6-trimethylphenol arepreferred.

The oxidation method includes a method in which an oxygen gas or air isdirectly used. Further, an electrode-oxidation method may be used. Anymethods may be used, and the oxidation method is not specially limited.In view of safety and low-cost investment in plant and equipment, airoxidation is preferred. A catalyst used when the oxidationpolymerization is carried out by the use of an oxygen gas or air,includes copper salts such as CuCl, CuBr, CU₂SO₄, CUCl₂, CuBr₂, CuSO₄and CuI. These catalysts may be used alone or in combination. Thesecatalysts may be used in combination with one amine or two or moreamines. The amine includes mono- and dimethylamines, mono- anddiethylamines, mono-and dipropyl amines, mono- and di-n-butylamines,mono- and di-sec-dipropylamines, mono- and dibenzylamines, mono-anddicyclohexylamines, mono- and diethanolamines, ethylmethylamine,methylpropylamine, butyldimethylamine, allylethylamine,methylcyclohexylamine, morpholine, methyl-n-butylamine,ethylisopropylamine, benzyl methyl amine, octylbenzylamine,octyl-chlorobenzylamine, methyl(phenylethyl)amine, benzylethylamine,N-n-butyldimethylamine, N,N′-di-tert-butylethylenediamine,di(chlorophenylethyl)amine, 1-methylamino-4-pentene, pyridine,methylpyridine, 4-dimethylaminopyridine and piperidine. The catalystsshall not be limited thereto and any other copper salts and amines maybe used.

Examples of a solvent for the reaction includes an aromatic hydrocarbonsolvent such as toluene, benzene or xylene or a halogenated hydrocarbonsolvent such as methylene chloride, chloroform or carbon tetrachloride.An alcohol solvent or a ketone solvent may be used in combination withthese solvents. The alcohol solvent includes methanol, ethanol, butanol,propanol, methyl propylene diglycol, diethylene glycol ethyl ether,butyl propylene glycol and propyl propylene glycol. The ketone solventincludes acetone, methyl ethyl ketone, diethyl ketone, methyl butylketone and methyl isobutyl ketone. Further, tetrahydrofurane and dioxanemay be used. The solvents shall not be limited to these.

Although the reaction temperature is not specially limited, it ispreferably 25 to 50° C. Since oxidation polymerization is an exothermicreaction, the control of a temperature is difficult and it is hard tocontrol a molecular weight when the reaction temperature is more than50° C. When the reaction temperature is lower than 25° C., the reactionrate becomes extremely slow, so that efficient production becomesimpossible.

At the Z sites of the formula (1) in the present invention 1, an organicgroup which has one or more carbon atoms and may contain an oxygen atomcan be located. Examples thereof include —(—CH₂—)—, —(CH₂—CH₂—)—, and—(—CH₂—Ar—O—)—, while the above organic group shall not be limitedthereto. The method for addition includes a method in which the organicgroups are directly added to the bifunctional PPE being an intermediateproduct represented by the formula (6) and a method using a halidehaving a long carbon chain at the time of synthesizing a derivative. Themethod shall not be limited to these methods.

For convenience' sake, the following explanations will be done on thebasis of a derivative from intermediate product represented by theformula (6) which is the simplest structure. The bifunctional PPEoligomer of the formula (6) is used as an intermediate product forproducing the thermosetting PPE oligomer compound. The bifunctional PPEoligomer can be used in the form of a powder separated from a reactionsolution or in the form of a solution thereof in a reaction solution.

An example of the process for producing the epoxy compound of thepresent invention 1 will be explained. The epoxy compound can besynthesized by dehydrohalogenation of the above bifunctional compoundhaving phenolic hydroxyl groups at terminals represented by the formula(6), as an intermediate product, and a halogenated glycidyl such asepichlorohydrin in the presence of a base.

Typical examples of the base include sodium hydroxide, potassiumhydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodiumcarbonate, potassium carbonate and sodium bicarbonate. The base shallnot be limited thereto.

The reaction temperature is preferably between −10° C. and 110° C.

An example of the production process for the allyl compound of thepresent invention 1 will be explained. The allyl compound can besynthesized by dehydrohalogenation of the above bifunctional compoundhaving phenolic hydroxyl groups at terminals represented by the formula(6), as an intermediate product, and an allyl halide such as allylbromide or allyl chloride in the presence of a phase transfer catalystunder a base condition.

Examples of the phase transfer catalyst include tertiary amines such astrimethylamine and tetramethylethylenediamine, quaternary ammonium saltssuch as tetrabutylammonium chloride, tetrabutylammonium bromide,tetrabutylammonium iodide, benzyltri-n-butylammonium chloride,benzyltri-n-butylammonium bromide and benzyl-n-butylammonium iodide andquaternary phosphonium salts. However, the phase transfer catalyst shallnot be limited thereto.

Examples of the base include sodium hydroxide, potassium hydroxide,sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate,potassium carbonate and sodium bicarbonate, while the base shall not belimited to these.

The reaction temperature is preferably between −10° C. and 60° C.

The thermosetting PPE oligomer compound of the present invention can becured alone or it can be cured as a resin composition further containingother cyanate compounds, an epoxy compound, other polymerizablecompounds or a catalyst.

Any known curing methods can be employed as a curing method. Examples ofthe above other cyanate compounds include m- or p-phenylenebiscyanate,1,3,5-tricyanatebenzene, 4,4′-dicyanatobiphenyl,3,3′5,5′-tetramethyl-4,4′-dicyanatebiphenyl,2,3,3′,5,5′-pentamethyl-4,4,-dicyanatebiphenyl,2,2′3,3′,5,5′-hexamethyl-4,4′-dicyanatebiphenyl,bis(4-cyanatephenyl)methane,1-(2,3,5-trimethyl-4-cyanatephenyl)-1-(3,5-dimethyl-4-cyanatephenyl)methane,bis(2,3,5-trimethyl-4-dicyanatephenyl)methane,1,1-bis(4-cyanatephenyl)ethane,1-(2,3,5-trimethyl-4-cyanatephenyl)-1-(3,5-dimethyl-4-cyanatephenyl)ethane,1,1-bis(2,3,5-trimethyl-4-dicyanatephenyl)ethane,2,2-bis(4-cyanatephenyl)propane,2-(2,3,5-trimethyl-4-cyanatephenyl)-2-(3,5-dimethyl-4-cyanatephenyl)propane,2,2-bis(2,3,5-trimethyl-4-dicyanatephenyl)propane,bis(4-cycanatephenyl)ether, bis(4-cyanatephenyl)sulfone,bis(4-cyanatephenyl)sulfide, 4,4′-dicyanatebenzophenone andtris(4-cyanatephenyl)methane. That is, the cyanate compounds arebiphenols to which an aromatic ring having a cyanate group directlybonds, bis or polycyanate compounds to which an aromatic ring having acyanate group bonds at a crosslinking portion, prepolymers of thesecyanate compounds, prepolymers of these cyanate compounds with diamines,and a cyanate-group-containing novolak type phenolic resin derived froma novolak resin which is a reaction product between phenols such asphenol and o-cresol and formaldehyde. These cyanate compounds may beused alone or in combination.

The above other polymerizable compounds include bismaleimide, an epoxyresin and the like. These may be used as a mixture thereof. Examples ofthe bismaleimide includes N,N′-diphenylmethanebismaleimide,N,N′-phenylenebismaleimide, N,N′-diphenyletherbismaleimide,N,N′-dicyclohexylmethanebismaleimide, N,N′-xylenebismaleimide,N,N′-diphenylsulfonebismaleimide, N,N′-tolylenebismaleimide,N,N′-xylylene bismaleimide, N,N′-diphenylcyclohexane bismaleimide,N,N′-dichloro-diphenylmethane bismaleimide, N,N′-diphenylcyclohexanebismaleimide, N,N′-diphenylmethane bismethylmaleimide,N,N′-diphenyletherbismethylmaleimide,N,N′-diphenylsulfonebismethylmaleimide, N,N′-ethylenebismaleimide,N,N′-hexamethylenebismethylmaleimide, prepolymers of theseN,N′-bismaleimide compounds, prepolymers of these bismaleimide compoundswith diamines, and maleimide-modified compounds ormethylmaleimide-modified compounds of aniline-formalin polycondensates.

Examples of the above epoxy resin include biphenol and a resin obtainedby substituting at least one position of the 2-, 2′-, 3-, 3′-, 5- and5′-positions of biphenol with a halogen atom, an alkyl group having 6 orless carbon atoms or a phenyl group; bisphenol A and a resin obtained bysubstituting at least one position of the 2-position, the 3-position andthe 5-position of bisphenol A with a halogen atom, an alkyl group having6 or less carbon atoms or a phenyl group; bisphenol F and a resinobtained by substituting at least one position of the 2-position, the3-position and the 5-position of bisphenol F with a halogen atom, analkyl group having 6 or less carbon atoms or a phenyl group; glycidylether compounds derived from bivalent or tri- or more-valent phenolssuch as hydroquinon, resorcin, tris-4-(hydroxyphenyl)methane and1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; a novolak type epoxy resinderived from a novolak resin which is a reaction product between phenolssuch as phenol and o-cresol and formaldehyde; amine type epoxy resinsderived from aniline, p-aminophenol, m-aminophenol, 4-amino-m-cresol,6-amino-m-cresol, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylether,3,4′-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene,1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane,p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine,2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine,1,4-cyclohexane-bis(methylamine),5-amino-1-(4′-aminophenyl)-1,3,3-trimethylindane,6-amino-1-(4′-aminophenyl)-1,3,3-trimethylindane and the like; glycidylester compounds derived from aromatic carboxylic acids such asp-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalicacid; hydantoin type epoxy resins derived from 5,5-dimethylhydantoin andthe like; alicyclic epoxy resins such as2,2-bis(3,4-epoxycyclohexyl)propane,2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexenedioxideand 3,4 -epoxycyclohexylmethyl-3,4 -epoxycyclohexane carboxylate;triglycidyl isocyanurate, and 2,4,6-triglycidoxy-S-triazine. These epoxyresins may be used alone or in combination.

The above resin composition may contain a curing agent for each of theingredients. When the epoxy compound of the present invention is used orthe resin composition contains an epoxy resin in a constitution, theremay be used, as a curing agent, dicyandiamide, tetramethylguanidine, anaromatic amine, a phenol novolak resin, a cresol novolak resin, acidanhydride, and various aliphatic and alicyclic amines. In this case, thecuring agents maybe used alone or in combination. As an aromatic amine,the above aromatic diamines are typical. As a curing agent used when theresin composition contains a cyanate compound or bismaleimide, the abovearomatic diamines and alicyclic diamines are typical. Each of the curingagents may be incorporated in the resin composition in the form of thecuring agent alone or may be incorporated in the resin composition inthe form of a prepolymer of an ingredient to which each curing agentcorresponds.

The above resin composition can be thermally cured in a comparativelyshort time without containing a catalyst. However, the use of a catalystcan decrease a molding temperature and shorten the curing time. Such acatalyst includes amines such as N,N-dimethylaniline, triethylenediamineand tri-n-butylamine, imidazoles such as 2-methylimidazole and2-ethyl-4-methylimidazole, phenols such as phenol and resorcin,organometallic salts such as cobalt naphthenate, lead stearate, tinoleate, tin octylate, zinc octylate and titanium butyrate, chloridessuch as aluminum chloride, tin chloride and zinc chloride, and chelatemetals. These catalysts may be used alone or in combination.

The above resin composition may contain an extending agent, a filler(including organic and inorganic fillers), a reinforcing agent or apigment as required. Examples of these include silica, calciumcarbonate, antimony trioxide, kaoline, titanium dioxide, zinc oxide,mica, barite, carbon black, polyethylene powder, polypropylene powder,glass powder, aluminium powder, iron powder, copper powder, glass fiber,carbon fiber, alumina fiber, asbestos fiber, aramid fiber, glass wovenfabric, glass unwoven fabric, aramid unwoven fabric and liquid crystalpolyester unwoven fabric. These may be used alone or in combination.

Further, the resin composition containing these is used for molding,lamination, an adhesive or a composite material such as a copper-cladlaminate. Particularly, when the cyanate compound alone, the epoxycompound alone or a combination of the cyanate compound and the epoxycompound is used, typical examples of uses are prepreg obtained bysemi-curing the resin and a laminate obtained by curing the aboveprepreg. Further, when the epoxy compound is used, a typical example isa use for a semiconductor sealing material.

The sealing epoxy resin composition of the present invention 2 will beexplained hereinafter.

According to the present invention 2, there is provided a sealing epoxyresin composition capable of giving a sealing layer which is free fromthe occurrence of cracks, when exposed to a high temperature such as asolder reflow, and has a low dielectric constant.

That is, the sealing epoxy resin composition of the present invention 2is a resin composition containing as ingredients an epoxy resin, acuring agent, an inorganic filler and a polyphenylene ether oligomercompound having a number average molecular weight of 700 to 3,000 andhaving an epoxy group at each terminal, represented by the formula (9),

-   -   wherein —(O—X—O)—, —(Y—O)—, Z, A and i are as defined in the        formula (1), each of a and b is 0 or an integer of 1 to 20,        provided that at least either a or b is not 0, each of c and d        is 0 or an integer of 1 to 20, provided that at least either c        or d is not 0, and j is 0 or an integer of 1 to 5.

According to the present invention 2, further, there is provided asealing epoxy resin composition according to the above, wherein, in thepolyphenylene ether oligomer compound having an epoxy group at eachterminal represented by the formula (9), at least R₁, R₂, R₇ and R₈ inthe formula (2) representing —(O—X—O)— are a methyl group and —(Y—O)— isan arrangement of the formula (4) or the formula (5) or a randomarrangement of the formula (4) and the formula (5).

According to the present invention 2, there is provided a sealing epoxyresin composition according to the above, wherein the content of thepolyphenylene ether oligomer compound having an epoxy group at eachterminal, represented by the formula (9), in the sealing epoxy resincomposition is in the range of from 1 to 60% by weight based on thetotal amount of the epoxy resin, the curing agent and the polyphenyleneether oligomer compound having an epoxy group at each terminal.

According to the present invention 2, there is provided a sealing epoxyresin composition according the above, wherein the content of theinorganic filler in the sealing epoxy resin composition is in the rangeof from 15 to 95% by weight based on the total amount of the epoxyresin, the curing agent, the inorganic filler and the polyphenyleneether oligomer compound having an epoxy group at each terminal.

Since the epoxy resin composition of the present invention 2 containsthe polyphenylene ether oligomer compound having an epoxy group at eachterminal, it has a low dielectric constant and excellent mechanicalstrength and the melt viscosity of the resin composition can bedecreased. When the melt viscosity of the above resin composition islow, resin flowability is good at a sealing-molding time and no voidsoccur, so that moldability is excellent.

The epoxy resin may be a biphenyl type epoxy resin alone and may be amixture of the biphenyl type epoxy resin with a cresol novolak typeepoxy resin, a naphthalene skeleton type epoxy resin, a bisphenol A typeepoxy resin, a bisphenol F type epoxy resin or a flame-retardant epoxyresin obtained by brominating any one of these epoxy resins.

Then, the polyphenylene ether oligomer compound having an epoxy group ateach terminal (to be referred to as “bifunctional OPE-2Ep” hereinafter)used in the present invention 2 will be explained.

The above bifunctional OPE-2Ep is obtained by dehydrohalogenation of apolyphenylene ether oligomer (to be referred to as “bifunctional OPE”hereinafter) of the formula. (6) shown in the present invention 1, whichis obtained by oxidative copolymerization of a bivalent phenol and amonovalent phenol, and a halogenated glycidyl such as epiohlorohydrin inthe presence of a base. The oxidation method, the reaction solvent andthe reaction temperature, etc., are the same as those described in thepresent invention 1.

At the Z positions of the formula (9) in the present invention 2, anorganic group which has one or more carbon atoms and may contain anoxygen atom can be located. Examples thereof include —(—CH₂—)—,—(CH₂—CH₂—)—, and —(—CH₂—Ar—O—)—, while the above organic group shallnot be limited thereto. The method for addition includes a method inwhich the organic groups are directly added to the bifunctional OPErepresented by the formula (6) and a method using a halide having a longcarbon chain at the time of synthesizing a derivative, while the methodshall not be limited to these methods.

For convenience' sake, the following explanations will be done on thebasis of a derivative from the bifunctional OPE represented by theformula (6) which is the simplest structure. The bifunctional OPE of theformula (6) is used for producing the bifunctional OPE-2Ep. Thebifunctional OPE may be used in the form of a powder separated from areaction solution or in the form of a solution thereof in a reactionsolution.

An example of the process for producing the bifunctional OPE-2Ep of thepresent invention will be shown. The bifunctional OPE-2Ep can besynthesized by dehydrohalogenation of the above compound having phenolichydroxyl groups at both terminals, represented by the formula (6), and ahalogenated glycidyl such as epichlorohydrin in the presence of a base.As the base, the same bases as those described in the present invention1 are used. The reaction is preferably carried out at a reactiontemperature between −10° C. and 110° C.

The number average molecular weight of the bifunctional OPE-2Ep islimited in the range of from 700 to 3,000. When the above number averagemolecular weight exceeds 3,000, the melt viscosity of the resincomposition increases. When it is smaller than 700, mechanical strengthor heat resistance is decreased. The bifunctional OPE-2Ep has a low meltviscosity so that its flowability is high. It is excellent incompatibility with an epoxy resin. Further, since it has epoxy groups atboth terminals, the resin composition has good adhesive properties andits sealing layer is further excellent in strength under heat. As aresult thereof, when the sealing layer is exposed to a high temperatureat soldering or the like, the occurrence of cracks can be prevented.Further, since a polyphenylene ether resin is a material having lowdielectric characteristics, a sealing layer having a low dielectricconstant can be formed.

In the sealing epoxy resin composition of the present invention 2, thecontent of the bifunctional OPE-2Ep is preferably in the range of fromto 60% by weight, more preferably 5 to 50% by weight, based on the totalamount of the epoxy resin, the bifunctional OPE-2Ep and the curingagent. When the above content is lower than 1% by weight, cracks are aptto occur in the sealing layer. When the above content is higher than 60%by weight, the melt viscosity increases at a sealing-molding so thatvoids occur and moldability is decreased.

Examples of the inorganic filler which is an ingredient of the sealingepoxy resin composition of the present invention 2 include inorganicpowders such as silica and alumina. The preferable content of theinorganic filler varies depending upon a use. For example, concerning ause as a sealing material for a potting molding, the content of theinorganic filler is preferably in the range of from 15 to 60% by weight,more preferably from 20 to 50% by weight, based on the total amount ofthe epoxy resin, the bifunctional OPE-2Ep, the curing agent and theinorganic filler. In this case of the use as a sealing material for apotting molding, when the content of the above inorganic filler is lessthan 15% by weight, the strength of a sealing layer is low. When theabove content is more than 60% by weight, moldability decreases at asealing-molding.

Further, concerning a use as a sealing material for a injection-molding,the content of the inorganic filler is preferably in the range of from60 to 95% by weight, more preferably from 70 to 90% by weight, based onthe total amount of the epoxy resin, the bifunctional OPE-2Ep, thecuring agent and the inorganic filler. In this case of the use as asealing material for a injection-molding, when the content of the aboveinorganic filler is less than 70% by weight, the moisture absorptioncoefficient of a sealing layer increases so that cracks are apt tooccur. When the above content is more than 95% by weight, the meltviscosity increases at a sealing-molding so that voids occur andmoldability decreases.

The above inorganic filler is preferably surface-treated with a couplingagent for improving the conformability with the epoxy resin. Examples ofthe coupling agent include silane coupling agents such asγ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane andN-phenyl-γ-aminopropyltrimethoxysilane.

The sealing epoxy resin composition may contain a curing accelerator, areleasing agent, a coloring agent, a flame retardant and a stressreducing agent, as required, in addition to the epoxy resin, thebifunctional OPE-2Ep, the curing agent and the inorganic filler.

Examples of the curing accelerator include tertiary amines such as1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine andbenzyldimethylamine, imidazoles such as 2-methylimidazole,2-ethyl-4-methylimidazole, 2-phenylimidazole and2-phenyl-4-methylimidazole, and organic phosphines such astributylphosphine and triphenylphosphine. Of these, triphenylphosphineimproves the electric characteristics of a sealing layer and thereforetriphenylphosphine is preferred.

Examples of the releasing agent include carnauba wax, stearic acid,montanoic acid and a carboxyl group-containing polyolefine. Examples ofthe coloring agent include carbon black. Examples of the above flameretardant include antimony trioxide. Examples of the stress reducingagent include silicone gel, silicone rubber and silicone oil.

The epoxy resin composition for laminates, provided by the presentinvention 3, will be explained hereinafter.

According to the present invention 3, there are provided an epoxy resincomposition for laminates which is excellent in dielectriccharacteristics, moldability and heat resistance, prepreg and a printedwiring board.

According to the present invention 3, there is provided an epoxy resincomposition for laminates which contains as ingredients a polyphenyleneether oligomer epoxy compound having a number average molecular weightof 700 to 3,000 and having an epoxy group at each terminal, representedby the formula (9) shown in the present invention 2, and a curing agent.

According to the present invention 3, further, there is provided anepoxy resin composition for laminates, which composition contains apolyphenylene ether oligomer epoxy compound having a number averagemolecular weight of 700 to 3,000 and having an epoxy group at eachterminal, represented by the formula (9) shown in the present invention2, and a cyanate ester resin.

According to the present invention 3, there is provided an epoxy resincomposition for laminates according to the above, wherein in thepolyphenylene ether oligomer epoxy compound having an epoxy group ateach terminal represented by the formula (9), at least R₁, R₂, R₇ and R₈in the formula (2) representing —(O—X—O)—, shown in the presentinvention 1, are a methyl group and —(Y—O)— is an arrangement of theformula (4) shown in the present invention 1 or the formula (5) shown inthe present invention 1 or a random arrangement of the formula (4) andthe formula (5).

According to the present invention 3, since the above epoxy resincomposition contains the polyphenylene ether oligomer epoxy compoundhaving an epoxy group at each terminal represented by the formula (9),it has a low dielectric constant and excellent flexibility and the meltviscosity of the resin composition can be decreased. When the meltviscosity of the resin composition is low, the embeddability of theresin is good at a laminate-molding time and no voids occur so thatmoldability is excellent.

The number average molecular weight of the obtained bifunctional OPE-2Epused in the present invention 3 is limited in the range of from 700 to3,000. When the above number average molecular weight exceeds 3,000, themelt viscosity of the resin composition increases. When it is smallerthan 700, mechanical strength or heat resistance is decreased. The abovebifunctional OPE-2Ep has a low melt viscosity so that its flowability ishigh. It is excellent in compatibility with a different resin. Further,since it has epoxy groups at both terminals, the resin composition hasgood adhesive properties. As a result thereof, when the resincomposition is exposed to a high temperature at soldering or the likeafter moisture absorption, the occurrence of swelling is prevented.Further, since a polyphenylene ether resin is a material having lowdielectric characteristics, there can be provided a laminate having lowdielectric characteristics.

The curing agent, which is an ingredient of the epoxy resin compositionfor laminates provided by the present invention 3, includes generallyused curing agents such as amine type curing agents typified by primaryamine and secondary amine, phenol type curing agents typified bybisphenol A and phenol novolak, acid anhydride type curing agents, andcyanate-ester type curing agents. These curing agents may be used aloneor in combination.

The bifunctional OPE-2Ep composition of the present invention 3 can beused in combination with various resins according to a purpose or use.Specific examples of the resins include various epoxy resins; modifiedepoxy resins, oxetane resins, (meth)acrylic acid esters; polyallylcompounds such as diallyl benzene and diallyl terephthalate; vinylcompounds such as N-vinyl-2-pyrolidone and divinyl benzene;polymerizable double-bond-containing monomers such as unsaturatedpolyester; polyfunctional maleimides; polyimides; rubbers such aspolybutadiene, thermoplastic resins such as polyethylene andpolystyrene; engineering plastics such as a ABS resin and polycarbonate;and a cyanate ester resin. The above resins shall not be limited tothese resins.

Further, the resin composition may contain various additives such as aknown inorganic or organic filler, a dye, a pigment, a thickener, alubricant, an antifoamer, a coupling agent, a photosensitizer, anultraviolet absorber and a flame retardant, as required.

Examples of the epoxy resin used in the present invention 3 includebisphenol A type epoxy, bisphenol F type epoxy, bisphenol Z type epoxy,biphenol.epoxy, tetramethylbiphenol.epoxy, hexamethylbiphenol.epoxy,xylene novolak.epoxy, biphenyl novolak.epoxy, dicyclopentadienenovolak.epoxy, phenol novolak.epoxy, cresol novolak.epoxy, andflame-retardant epoxy resins obtained by brominating these epoxy resins.There may be used a composition containing one epoxy resin or two ormore epoxy resins selected from these epoxy resins as required and areaction product of these epoxy resins.

Examples of the cyanate ester compound used in the present invention 3include 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-,1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene,1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl,bis(4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane,2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether,bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone,tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl)phosphate,4,4′-dicyanato-3,3′,5,5′-tetramethylbiphenyl,4,4′-dicyanato-2,2′,3,3′,5,5′-hexamethylbiphenyl, and cyanates obtainedby a reaction of novolak with cyanogen halide.

Although the composition of the present invention 3 undergoes curingitself by heating, a heat-curing catalyst can be incorporated in thecomposition for increasing the curing rate and improving workability andeconomic efficiency. There may be used a heat-curing catalyst generallyknown as a heat-curing catalyst for a resin to be used in combination.

A copper-clad laminate using the bifunctional OPE-2Ep composition of thepresent invention 3 is particularly suitably used for a printed wiringboard which is required to have low dielectric characteristics. Thecopper-clad laminate of the present invention can be produced by ageneral method. That is, it is a method in which a base material isimpregnated with a resin varnish which is a solution of a thermosettingresin composition in an organic solvent, the base material isheat-treated to obtain prepreg, and then the prepreg and a copper foilare laminated and molded under heat to obtain a copper-clad laminate.However, the production method of the copper-clad laminate of thepresent invention shall not be limited to this method.

The organic solvent to be used includes acetone, methyl ethyl ketone,ethylene glycol monomethyl ether acetate, propylene glycol dimethylether, toluene, xylene, tetrahydrofuran and N,N-dimethylformamide. Thesolvent is not specially limited and various organic solvents may beused. These solvents may be used alone or in combination. The basematerial to be impregnated with the resin varnish includes all basematerials used for a thermosetting resin laminate. Example thereofincludes inorganic base materials such as a glass cloth and a glassunwoven fabric; and organic base materials such as a polyamide unwovenfabric and a liquid crystalline polyester unwoven fabric. For utilizingthe low dielectric characteristics of the present invention, it is moreeffective to use a base material having excellent dielectriccharacteristics such as D glass cloth or NE glass cloth.

The heat-treatment of the prepreg is properly selected depending uponthe kinds and the amounts of a solvent used, a resin constitution, acatalyst added and other additives, while it is generally carried out ata temperature of 100 to 250° C. for 3 to 30 minutes. The method oflaminating and heating the prepreg and the copper foil varies dependingupon the kind of the prepreg and the form of the copper foil. Generally,these materials are preferably thermally press-molded in vacuum at atemperature of 170 to 230° C. under a pressure of 10 to 30 kg/cm² for 40to 120 minutes.

The present invention 4 will be explained here in after.

According to the present invention 4, there are provided a novel(meth)acrylate compound having excellent heat resistance, a lowdielectric constant and a low dielectric loss tangent and a curableresin composition.

The (meth)acrylate compound of the present invention 4 is represented bythe formula (10),

-   -   wherein R₁ is a hydrogen atom or a methyl group, —(O—X—O)— is        represented by the formula (11) in which R₂, R₃, R₈ and R₉ may        be the same or different and are a halogen atom, an alkyl group        having 6 or less carbon atoms or a phenyl group, R₄, R₅, R₆ and        R₇ may be the same or different and are a hydrogen atom, a        halogen atom, an alkyl group having 6 or less carbon atoms or a        phenyl group and A is a linear, branched or cyclic hydrocarbon        having 20 or less carbon atoms, —(Y—O)— is an arrangement of one        kind of structure defined by the formula (12) or a random        arrangement of two or more kinds of structures defined by the        formula (12) in which R₁₀ and R₁₁ may be the same or different        and are a halogen atom, an alkyl group having 6 or less carbon        atoms or a phenyl group and R₁₂ and R₁₃ may be the same or        different and are a hydrogen atom, a halogen atom, an alkyl        group having 6 or less carbon atoms or a phenyl group, Z is an        organic group which has no OH group in a side chain and has one        or more carbon atoms and which may contain an oxygen atom, each        of a and b is 0 or an integer of 1 to 300, provided that at        least either a or b is not 0, and each of c and d is 0 or an        integer of 1.

Further, the present invention 4 provides a curable resin compositioncontaining the above (meth)acrylate compound and a cured product of theabove resin composition.

In the formula (10), examples of -(Z-O—)— include —((CH₂)_(m)—O—)—,—(CH₂CHRO)_(n)— and —(CH₂—Ar—O)—, while it shall not be limited tothese. The method of addition includes a method in which -(Z-O—)— isdirectly added to an intermediate represented by the formula (6) and amethod using a halide, while it shall not limited to these methods.

The method of producing the (meth)acrylate compound of the formula (10),provided by the present invention, is not specially limited. The(meth)acrylate compound of the formula (10) may be produced by anymethods. For example, the (meth)acrylate compound of the formula (10) isobtained by reacting a compound of the formula (13) with a (meth)acrylicacid or a (meth)acrylic acid derivative. Concretely, the (meth)acrylatecompound of the formula (10) is obtained by reacting a compound of theformula (13) with (meth)acrylic acid in the presence of anesterification catalyst such as p-toluenesulfonic acid, trifluoromethanesulfonic acid or sulfuric acid or its acid halide in the presence of,for example, an organic amine, sodium hydroxide or sodium carbonate, inthe presence of a solvent such as, preferably, toluene, xylene,cyclohexane, n-hexane, n-heptane or a mixture of these at a temperatureof preferably from 70° C. to 150° C.

-   -   wherein —(O—X—O)—, A, —(Y—O)—, Z, a, b, c and d are as defined        in the formula (10).

The compound of the formula (13) is obtained by producing the compoundof the formula (6) according to, for example, the method disclosed inJapanese Patent Application No. 2002-018508 and then introducing -(Z-O)—into it as required.

Cases in which, for example, —(CH₂)_(m)O— or —(CH₂CHR₁₄O)_(n)— isintroduced as -(Z-O)—, will be explained. —(CH₂)_(m)O— is introduced byreacting a compound of the formula (13) with a halogenated alcoholrepresented by the formula (14) in a proper solvent such as an alcohol,ether or a ketone in the presence of an alkaline catalyst such as KOH,K₂CO₃ or NaOEt, and —(CH₂CHR₁₄O)_(n)— is introduced by reacting acompound of the formula (13) with alkylene oxide represented by theformula (15) in a benzene type solvent such as benzene, toluene orxylene in the presence of an alkaline catalyst such as KOH, NaOEt ortriethylamine according to, for example, the method disclosed inJP-B-52-4547.X—(CH₂)_(m)—OH   (14)wherein X is Cl or Br and m is an integer of 2 or more.

wherein R₁₄ is a hydrogen atom, a methyl group or an ethyl group.

Next, the curable resin composition of the present invention 4 will beexplained. The curable resin composition is characterized in that itcontains the above (meth)acrylate compound of the present invention 4.The curable resin composition of the present invention may contain aknown epoxy resin, an oxetane resin, a compound having an ethylenicunsaturated group, a photpolymerization initiator and/or a thermalpolymerization initiator, and a photosensitizer.

The epoxy resin can be selected from generally known epoxy resins.Examples of the epoxy resin include a bisphenol A type epoxy resin, abisphenol F type epoxy resin, a biphenyl type epoxy resin, a phenolnovolak type epoxy resin, a cresol novolak type epoxy resin, a xylenenovolak type epoxy resin, triglycidyl isocyanurate, an alicyclic epoxyresin, a dicyclopentadiene novolak type epoxy resin, a biphenyl novolaktype epoxy resin and epoxy resins having a PPE structure disclosed inJapanese patent application Nos. 2001-353194 and 2002-018508. Theseepoxy resins may be used alone or in combination.

The oxetane resin can be selected from generally known oxetane resins.Examples of the oxetane resin include alkyl oxetanes such as oxetane,2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane and3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane,3,3′-di(trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane,3,3-bis(chrolomethyl)oxetane, OXT-101 (trade name, supplied by TOAGOSEICo., Ltd.) and OXT-121 (trade name, supplied by TOAGOSEI Co., Ltd.).These oxetane resins may be used alone or in combination.

When the epoxy resin and/or the oxetane resin are used in the curableresin composition of the present invention 4, an epoxy resin curingagent and/or an oxetane resin curing agent may be used. The epoxy resincuring agent is selected from generally known curing agents. Examples ofthe epoxy resin curing agent include imidazole derivatives such as2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole,1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole,2-phenyl-4,5-dihydroxymethylimidazole and2-phenyl-4-methyl-5-hydroxymethylimidazole; amine compounds such asdicyandiamide, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine,diaminodiphenyl methane and diaminodiphenyl sulfone; and phosphinecompounds such as phosphonium compounds. The oxetane resin curing agentcan be selected from known cationic polymerization initiators.Commercially available examples include SAN-AID SI-60L, SAN-AID SI-80L,SAN-AID SI-100L (supplied by Sanshin Chemical IndustryCo., Ltd.),CI-2064 (supplied by Nippon Soda Co., Ltd.), IRGACURE261 (supplied byCiba Specialty Chemicals), ADEKAOPTMER SP-170, ADEKAOPTMER SP-150,(supplied by Asahi Denka Kogyo K. K.), and CYRACURE UVI-6990 (suppliedby Union Carbide Corporation). The cationic polymerization initiatorsmay be used as an epoxy resin curing agent. These curing agents may beused alone or in combination.

The compound having an ethylenic unsaturated group can be selected fromgenerally known compounds having an ethylenic unsaturated group.Examples thereof include (meth)acrylates of monohydric and polyhydricalcohols such as 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, polypropylene glycol di(meth)acrylate,trimethylol propane di(meth)acrylate, trimethylol propanetri(meth)acrylate, pentaerythritol tetra(meth)acrylate anddipentaerythritol hexa(meth)acrylate, and epoxy(meth)acrylates such as abisphenol A type epoxy(meth)acrylate, a bisphenol F typeepoxy(meth)acrylate and epoxy(meth)acrylates having a PPE structuredisclosed in Japanese patent application Nos. 2001-387968 and2002-038156. These compounds having an ethylenic unsaturated group maybe used alone or in combination.

The photopolymerization initiator can be selected from generally knownphotopolymerization initiators. Examples of the photopolymerizationinitiator include α-diketones such as benzyl and diacetyl, acyloinethers such as benzoyl ethyl ether and benzoin isopropyl ether,thioxanthones such as thioxanthone, 2,4-diethylthioxanthone and2-isopropylthioxanthone, benzophenones such as benzophenone and4,4′-bis(dimethylamino)benzophenone, acetophenones such as acetophenone,2,2′-dimethoxy-2-phenylacetophenone and β-methoxy acetophenone, andaminoacetophenones such as2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-on e and2-benzyl-2-dimethylamino-1-(-4-morpholinophenyl)-butanone-1. Thesephotopolymerization initiators are used alone or in combination.

Further, the photopolymerization initiator may be used in combinationwith one kind of or two or more kinds of known photosensitizer(s).Examples of the photopolymerization initiator includeN,N-dimethylaminoethylbenzoate, N,N-dimethylaminoisoamylbenzoate,triethanolamine and triethylamine.

The thermal polymerization initiator may be selected from generallyknown thermal polymerization initiators. Examples thereof includeperoxides such as benzoyl peroxide, p-chlorobenzoyl peroxide,di-t-butylperoxide, diisopropyl peroxy carbonate anddi-2-ethylhexylperoxycarbonate, and azo compounds such asazobisisobutylonitrile.

Further, when the curable resin composition of the present invention isproduced, there may be added a known additive such as an inorganicfiller, a color pigment, an antifoamer, a surface conditioner, a flameretardant, an ultraviolet absorber, an antioxidant, a polymerizationinhibitor or a flow regulator, as required. Examples of the inorganicfiller include silicas such as natural silica, fused silica andamorphous silica, white carbon, titanium white, aerosil, alumina, talc,natural mica, synthetic mica, kaolin, clay, aluminum hydroxide, bariumsulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, T-glass,NE-glass and M-glass G20. The thus-obtained curable resin composition issuitable for various uses such as a solder resist composition, buildupwiring board materials, insulating coatings, adhesives, printing inksand coating materials.

The cured product of the present invention can be obtained by curing thecurable resin composition of the present invention, obtained by theabove method, according to a known curing method such as a method usingan electron beam, ultraviolet light or heat. When ultraviolet light isused for the curing, there may be used a low-pressure mercury lamp, anintermediate-pressure mercury lamp, a high-pressure mercury lamp, anultrahigh-pressure mercury lamp, a xenon lamp and a metal halide lamp asa light source for ultraviolet light.

The present invention 5 will be explained hereinafter.

According to the present invention 5, there are provided a novelepoxy(meth)acrylate compound having excellent heat resistance, a lowdielectric constant and a low dielectric loss tangent and a curableresin composition.

According to the present invention 5, there is provided a (meth)acrylatecompound represented by the formula (16),

-   -   wherein R₁, —(O—X—O)—, A, —(Y—O)—, a, b, c and d are as defined        in the formula (10), Z is an organic group having one or more        carbon atoms and may contain an oxygen atom, and n is 0 or an        integer of 1 to 10.

According to the present invention 5, there is provided anepoxy(meth)acrylate compound according to the above, wherein, in theformula (16), R₂, R₃, R₈ and R₉ in —(O—X—O)— are a methyl group, and—(Y—O)— has an arrangement structure of the formula (4) recited in thepresent invention 1 or the formula (5) recited in the present invention1 or a random arrangement structure of the formula (4) and the formula(5).

According to the present invention 5, further, there is provided anacid-modified epoxy(meth)acrylate compound obtained by reacting anepoxy(meth)acrylate compound represented by the formula (16) with acarboxylic acid or its anhydride. Further, there are provided a curableresin composition containing the above epoxy(meth)acrylate compoundand/or the acid-modified epoxy(meth)acrylate compound and a curedproduct thereof.

The epoxy(meth)acrylate compound of the formula (16) is preferablyproduced according to a known method, for example a method disclosed inJP-B-44-31472 or JP-B-45-1465. That is, typically, for example, theepoxy,(meth)acrylate compound of the formula (16) can be obtained byreacting an epoxy compound represented by the formula (9′) with anacrylic acid, a methacrylic acid or a mixture of an acrylic acid and amethacrylic acid. The epoxy compound of the formula (9′) is produced by,for example, the method disclosed in Japanese Patent Application No.2002-018508.

-   -   wherein —(O—X—O)—, A, —(Y—O)—, a, b, c and d are as defined in        the formula (10), Z is an organic group which has one or more        carbon atoms and which may contain an oxygen atom, and n is 0 or        an integer of 1 to 10

When the epoxy(meth)acrylate compound of the formula (16) in the presentinvention is produced, the amount of the acrylic acid, the methacrylicacid or a mixture of these based on the epoxy resin of the formula (9′)is not specially limited. Preferably, the amount of the acrylic acid,the methacrylic acid or the mixture of these per 1 chemical equivalentof an epoxy group of the epoxy compound composition is 0.1 to 5 chemicalequivalents, more preferably 0.3 to 3 chemical equivalents.

In the reaction, it is preferable to add a diluent. Examples of thediluent include alcohols such as methanol, ethanol, propanol, butanol,ethylene glycol, methyl cellosolve, ethylcellosolve, dipropylene glycolmonomethyl ether and diethylene glycol monomethyl ether, esters such asmethyl cellosolve acetate, ethylcellosolve acetate, dipropylene glycolmonomethyl ether acetate, diethylene glycol monomethyl ether acetate anddiethylene glycol monoethyl ether acetate, ketone solvents such asmethyl ethyl ketone and methyl isobutyl ketone, and aromatic compoundssuch as benzene, toluene, xylene, chlorobenzene, dichlorobenzene andsolvent naphtha.

Further, it is preferable to use a catalyst for promoting the reaction.Preferable concrete examples of the catalyst include amines such astriethylamine, dimethylbutyl amine and tri-n-butyl amine, quaternaryammonium salts such as tetramethylammonium salt, tetraethylammoniumsalt, tetrabutylammonium salt and benzyltriethylammonium salt,quaternary phosphonium salts, phosphines such as triphenylphosphine, andimidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole. Theamount of the catalyst based on a mixture of reaction raw materials ispreferably 0.1 to 10% by weight, more preferably 0.2 to 3% by weight.Further, it is preferred touseapolymerization inhibitor for preventing apolymerization during the reaction. Examples of the polymerizationinhibitor include hydroquinone, methyl hydroquinone, hydroquinonemonomethyl ether, 4-methylquinoline and phenothiazine. Further, forinhibiting a polymerization reaction due to unsaturated bonds, thereaction can be carried out under a flow of air or the like according tocircumstances. In this case, an antioxidant such as2,6-di-t-butyl-4-methylphenol may be used for preventing an oxidationreaction due to the air.

Although the reaction temperature varies depending upon the catalyst,preferred is a temperature at which the reaction of the epoxy compoundof the formula (9′) with the acrylic acid or the methacrylic acidadvances and no thermal polymerizations of raw materials, anintermediate product and a generation product occur. More preferably,the reaction temperature is 60° C. to 150° C., particularly preferably70° C. to 130° C. Although the reaction time depends on the reactiontemperature, it is preferably 1 to 15 hours. After the completion of thereaction, an excess (meth)acrylic acid and an excess diluent may beremoved by distillation or other methods, or these materials can be usedwithout removing.

Next, the acid-modified epoxy(meth)acrylate compound of the presentinvention 5 will be explained. The acid-modified epoxy acrylate compoundof the present invention is produced by reacting the above epoxyacrylate compound obtained from the epoxy compound of the formula (9′)and acrylic acid, methacrylic acid or a mixture of these, with acarboxylic acid or its anhydride. The carboxylic acid is a monovalent orpolyvalent carboxylic acid and it is preferably a monovalent orpolyvalent aliphatic carboxylic acid or a monovalent or polyvalentaromatic carboxylic acid.

Examples of the carboxylic acid or its anhydride include maleic acid,succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid,hexahydrophthalic acid, methyltetrahydrophthalic acid,methylhexahydrophthalic acid, chlorendic acid, methyl nadic acid,trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid,3,3′4,4′-biphenyl tetracarboxylic acid, cyclohexane tetracarboxylicacid, butane tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylicacid, 3,3′4,4′-diphenyl sulfone tetracarboxylic acid, 4,4′-oxydiphthalicacid, cyclopentane tetracarboxylic acid, and anhydrides of these. Thecarboxylic acid or its anhydride shall not be limited to these examples.The amount of the carboxylic acid or its anhydride per 1 chemicalequivalent of a hydroxyl group in the above epoxyacrylate compound is0.01 to 1.2 chemical equivalents, preferably 0.05 to 1 chemicalequivalent.

At the time of the reaction, various known esterification catalysts, adiluent mentioned above, and the like may be further added as required.Although the reaction temperature is not specially limited, preferred isa temperature at which no thermal polymerization of the epoxy acrylatecompound, etc., as a raw material, occurs. It is preferably 60° C. to130° C. Although the reaction time depends on the reaction temperature,it is preferably 1 to 80 hours.

After the reaction, the acid-modified epoxy (meth)acrylate compound ofthe present invention can be separated by a known method such asdistillation. Further, the acid-modified epoxy acrylate compound of thepresent invention may contain an epoxy group in a molecule. That is, asdescribed before, when the amount of the acrylic acid, the methacrylicacid or the mixture of these based on the epoxy compound is adjusted toa desired amount within the above range, an unreacted epoxy group isleft in the obtained epoxy acrylate compound. The thus-obtained epoxyacrylate compound is further acid-modified, whereby an acid-modifiedepoxy acrylate compound having an epoxy group is obtained. The acidvalue of the acid-modified epoxy acrylate compound can be properlyadjusted as required. It is preferably 20 to 200 mgKOH/g, morepreferably 30 to 150 mgKOH/g.

Then, the curable resin composition of the present invention 5 will beexplained. The curable resin composition is characterized in that itcontains the above epoxy(meth)acrylate compound and/or the acid-modifiedepoxy(meth)acrylate compound of the present invention 5. The curableresin composition of the present invention 5 may contain a known epoxyresin, an oxetane resin, a compound having an ethylenic unsaturatedcompound, a photopolymerization initiator and/or a thermalpolymerization initiator, a photosensitizer and the like. As theepoxy(meth)acrylate compound and the acid-modified epoxy(meth)acrylatecompound of the present invention 5, the above reaction products may beused as they are.

The epoxy resin, the oxetane resin, an epoxy resin curing agent, anoxetane resin curing agent, the compound having an ethylenic unsaturatedcompound, the photopolymerization initiator, the thermal polymerizationinitiator, additives to be added to the resin composition, the curingmethod, etc., can be selected or carried out similarly to thedescriptions in the present invention 4.

The present invention 6 will be explained hereinafter.

According to the present invention 6, there is provided a thermosettingresin which has the excellent electric characteristics and toughness ofPPE and is improved in compatibility with a different resin and inmolding processability. Further, according to the present invention 6,there is provided a thermosetting resin which can be widely utilized forvarious uses including a use in an electronics field.

The present inventors have made diligent studies concerning athermosetting resin succeeding the excellent toughness of PPE and havinglow dielectric characteristics and as a result found the following. Acyanate resin obtained by dehydrohalogenation of a bifunctional PPE ofthe formula (6′), which is obtained by oxidative copolymerization of abivalent phenol and a monovalent phenol, and cyanogen halide such ascyanogen chloride in the presence of a base, has the above functions andeffects. On the basis of the above finding, the present inventors havecompleted the present invention 6.

According to the present invention 6, there are provided a thermosettingresin represented by the following formula (17), a resin composition forlaminates containing the above thermosetting resin, prepreg obtained byusing the above resin composition and a printed wiring board obtained byusing the above resin composition,

-   -   wherein —X— is represented by the formula (18) in which R₁, R₂,        R₇ and R₈ may be the same or different and are a halogen atom,        an alkyl group having 6 or less carbon atoms or a phenyl group,        R₃, R₄, R₅ and R₆ may be the same or different and are a        hydrogen atom, a halogen atom, an alkyl group having 6 or less        carbon atoms or a phenyl group and A is a cyclic hydrocarbon or        an organic group having an aromatic group, —(O—Y)— is        represented by the formula (19) in which R₉ and R₁₀ may be the        same or different and are a halogen atom, an alkyl group having        6 or less carbon atoms or a phenyl group and R₁₁ and R₁₂ may be        the same or different and are a hydrogen atom, a halogen atom,        an alkyl group having 6 or less carbon atoms or a phenyl group,        —(O—Y)— is an arrangement of one kind of structure defined by        the formula (19) or a random arrangement of two or more kinds of        structures defined by the formula (19), Z is an organic group        which has one or more carbon atoms and may contain an oxygen        atom, each of a and b is 0 or an integer of 1 to 300, provided        that at least either a or b is not 0, and each of i is        independently 0 or an integer of 1).

The present invention 6 will be explained in detail hereinafter.

The present invention 6 synthesizes a bifunctional PPE efficiently andprovides a thermosetting resin (cyanate compound) which has a higheractivity and which is to be incorporated into a network in a resinconstitution. Here, as raw materials, the same bivalent phenol andmonovalent phenol as those used in the present invention 1 are used.

The bifunctional PPE oligomer compound which is an intermediate productof the present invention 6 has a structure represented by the formula(6′) in which —X— is represented by the formula (18) and —(O—Y)— is anarrangement of one kind of structure defined by the formula (19) or arandom arrangement of two or more structures defined by the formula(19).

The PPE oligomer compound of the formula (6′) which is an intermediateproduct of the present invention 6 can be efficiently produced byoxidation polymerization of a bivalent phenol represented by the formula(7) shown in the present invention 1 and a monovalent phenol representedby the formula (8) shown in the present invention 1 or a mixture ofmonovalent phenols represented by the formula (8) similarly to thepresent invention 1.

An example of the process for producing the cyanate compound of thepresent invention 6 will be explained. The cyanate compound issynthesized by dehydrohalogenation of the above bifunctional compoundhaving phenolic hydroxyl groups at both terminals, represented by theformula (6′), as an intermediate product, and cyanogen halide such ascyanogen chloride or cyanogen bromide in the presence of a base.

Typical examples of the base include tertiary amines such astrimethylamine, triethylamine, tripropylamine, dimethylaniline andpyridine, sodium hydroxide, potassium hydroxide, sodium methoxide,sodium ethoxide, calcium hydroxide, sodium carbonate, potassiumcarbonate and sodium bicarbonate. The base shall not be limited thereto.

Typical examples of a solvent for the reaction includes toluene, xylene,chloroform, methylene chloride, carbon tetrachloride, chlorobenzene,nitrobenzene, nitromethane, acetone, methyl ethyl ketone,tetrahydrofuran, dioxane and water. The solvent shall not be limitedthereto.

When cyanogen chloride is used, the reaction temperature is preferablybetween −30° C. and +13° C. (boiling point). When cyanogen bromide isused, it is preferably between −30° C. and +65° C.

The thermosetting PPE oligomer compound of the present invention can becured alone. Otherwise, it can be cured as a resin compositioncontaining the thermosetting PPE oligomer compound, a different cyanatecompound, an epoxy compound, other polymerizable compounds or acatalyst.

As for the curing method, the different cyanate compound, the otherpolymerizable compounds, the epoxy resin, a curing agent, the catalyst,an extender to be added as required, etc., used in the present invention6, there may be employed those which have been described in the presentinvention 1.

Further, a composition using these is utilized for uses, e.g., molding,lamination, an adhesive and a composite material such as a copper-cladlaminate. When the cyanate compound is used alone or in combination,typical examples of uses are prepreg in which the resin or the resincomposition is semi-cured and a laminate obtained by curing the aboveprepreg.

In the present invention 6, there is provided a thermosetting resin inwhich, in —X— in the formula (17), R₁, R₂, R₃, R₇ and R₈ may be the sameor different and are a halogen atom, an alkyl group having 6 or lesscarbon atoms or a phenyl group, R₄, R₅ and R₆ may be the same ordifferent and are a hydrogen atom, a halogen atom, an alkyl group having6 or less carbon atoms or a phenyl group and A is a linear or branchedhydrocarbon having 20 or less carbon atoms, an aromatic group or anorganic group having a cyclic hydrocarbon.

In the present invention 6, further, there is provided a thermosettingresin in which at least R₁, R₂, R₇ and R₈ in —X— in the formula (17) areessentially a methyl group, further at least one of R₃, R₄, R₅ and R₆ issubstituted with a methyl group, and —(O—Y)— has an arrangementstructure of the formula (4) or the formula (5) or a random arrangementstructure of the formula (4) and the formula (5).

The present invention 6 further provides a resin composition forlaminates which contains a polyphenylene ether oligomer cyanate compoundhaving a number average molecular weight of 700 to 3,000 and havingcyanate groups at both terminals represented by the above formula (17)as an ingredient.

Further, the present invention 6 provides a resin composition forlaminates containing the polyphenylene ether oligomer cyanate compoundof the formula (17), a different cyanate ester resin and an epoxy resinas ingredients.

The present invention 6 further provides prepreg obtained by using theabove resin composition for laminates.

The present invention 6 further provides a printed wiring board obtainedby using the above prepreg.

The number average molecular weight of the obtained polyphenylene etheroligomer compound (to be referred to as “bifunctional OPE-2CN”hereinafter) is preferably limited in the range of from 700 to 3,000.When the above number average molecular weight exceeds 3,000, the meltviscosity of the resin composition increases. When it is smaller than700, mechanical strength or heat resistance is decreased. The abovebifunctional OPE-2CN has a low melt viscosity so that its flowability ishigh. It is excellent in compatibility with a different resin. Further,since it has cyanate groups at both terminals, the resin composition hasgood adhesive properties. As a result thereof, when the resincomposition is exposed to a high temperature at soldering or the likeafter moisture absorption, the occurrence of swellings can be prevented.Further, since a polyphenylene ether resin is a material having lowdielectric characteristics, there can be provided a laminate having lowdielectric characteristics.

In the resin composition for laminates, provided by the presentinvention, the content of the bifunctional OPE-2CN is preferably in therange of from 1 to 60% by weight, more preferably 5 to 50% by weight,based on the total amount of the bifunctional OPE-2CN, the epoxy resinand the different cyanate resin. When the above content is lower than 1%by weight, sufficient flexibility is not obtained. When the abovecontent is higher than 60% by weight, the melt viscosity increases sothat voids occur at a laminate-molding, which decreases moldability.

Examples of the cyanate resin, which is an ingredient of the resincomposition of the present invention 6, include 1,3- or1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-,2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene,4,4′-dicyanatobiphenyl, bis(4-cyanatophenyl)methane,2,2-bis(4-cyanatophenyl)propane,2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether,bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone,tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl)phosphate,4,4′-dicyanato-3,3′,5,5′-tetramethylbiphenyl,4,4′-dicyanato-2,2′,3,3′,5,5′-hexamethylbiphenyl, and cyanates obtainedby a reaction of novolak with cyanogen halide.

Examples of the epoxy resin, which is an ingredient of the resincomposition of the present invention 6, include bisphenol A type epoxy,bisphenol F type epoxy, bisphenol Z type epoxy, biphenol.epoxy,tetramethylbiphenol.epoxy, hexamethylbiphenol.epoxy, xylenenovolak.epoxy, biphenyl novolak.epoxy, dicyclopentadiene novolak.epoxy,phenol novolak.epoxy, cresol novolak-epoxy, and flame-retardant epoxyresins obtained by brominating these epoxy resins. Further, there may beused a composition containing one epoxy resin or two or more epoxyresins selected from the above epoxy resins as required and a reactionproduct of these epoxy resins. Further, a bifunctional polyphenyleneether oligomer epoxy compound disclosed in Japanese Patent ApplicationNo. 2001-353194 may be used in combination.

The resin composition for laminates, provided by the present invention6,may be used in combination with various resins according to a purposeand use. Specific examples of the resins include oxetane resins;(meth)acrylic acid esters; polyallyl compounds such as diallyl benzeneand diallyl terephthalate; vinyl compounds such as N-vinyl-2-pyrolidoneand divinyl benzene; polymerizable double-bond-containing monomers suchas unsaturated polyester; polyfunctional maleimides; polyimides; rubberssuch as polybutadiene, thermoplastic resins such as polyethylene,polystyrene and PPE; and engineering plastics such as ABS resin andpolycarbonate. The above resins shall not be limited to these resins.

Further, the resin composition may contain various additives such as aknown inorganic or organic filler, a dye, a pigment, a thickener, alubricant, an antifoamer, a coupling agent, a photosensitizer, anultraviolet absorber and a flame retardant, as required.

Although the composition of the present invention 6 undergoes curingitself under heat, a heat-curing catalyst can be incorporated in thecomposition for increasing the curing rate and improving workability andeconomic efficiency. There may be used a heat-curing catalyst generallyknown as a heat-curing catalyst for a resin to be used in combination.

A copper-clad laminate using the resin composition for laminates,provided by the present invention 6, is particularly suitably used for aprinted wiring board which is required to have low dielectriccharacteristics. The copper-clad laminate of the present invention 6 isproduced by a generally known method. That is, it is a method in which abase material is impregnated with a resin varnish which is a solution ofa thermosetting resin composition in an organic solvent, the basematerial is heat-treated to obtain prepreg, and then the prepreg and acopper foil are laminated and molded under heat to obtain a copper-cladlaminate. However, the production method of the copper-clad laminateshall not be limited to this method.

The organic solvent to be used includes acetone, methyl ethyl ketone,ethylene glycol monomethyl ether acetate, propylene glycol dimethylether, toluene, xylene, tetrahydrofuran and N,N-dimethylformamide. Thesolvent is not specially limited and various organic solvents may beused. These solvents may be used alone or in combination.

The base material to be impregnated with the resin varnish includes allbase materials used for a thermosetting resin laminate. Example thereofincludes inorganic base materials such as a glass cloth and a glassunwoven fabric; and organic base materials such as a polyamide unwovenfabric and a liquid crystalline polyester unwoven fabric. For utilizingthe low dielectric characteristics of the present invention, it is moreeffective to use a base material having excellent dielectriccharacteristics such as D glass cloth or NE glass cloth.

The heat-treatment of the prepreg is properly selected depending uponthe kinds and the amounts of a solvent used, a resin constitution, acatalyst added and other additives, while it is generally carried out ata temperature of 100 to 250° C. for 3 to 30 minutes. The method oflaminating and heating the prepreg and the copper foil varies dependingupon the kind of the prepreg and the form of the copper foil. Generally,these materials are preferably thermally press-molded in vacuum at atemperature of 170 to 230° C. under a pressure of 10 to 30 kg/cm² for 40to 120 minutes.

Effect of the Invention

It is confirmed that the thermosetting PPE oligomer compound of thepresent invention 1 has the excellent properties (low dielectriccharacteristics, toughness) of PPE, is high in the compatibility with adifferent resin and is to be incorporated into a network in a resinconstitution. Therefore, for example, a varnish for laminates can beeasily prepared and a laminate material excellent in moldingprocessability can be produced. Further, a cured product obtained fromthe oligomer compound alone or a mixture of the oligomer compound and adifferent resin accomplishes low dielectric characteristics and becomesan electric or electronic material having the excellent properties of aPPE polymer. It is confirmed that the compound of the present inventionhaving a phenylene ether structure is excellent in dielectriccharacteristics and heat resistance over a particular epoxy used forsealing a semiconductor, and it is found that the compound of thepresent invention is very useful.

An electronic part using the sealing epoxy resin composition of thepresent invention 2 is free from the occurrence of cracks, when exposedto a high temperature at a solder reflow or the like, and a sealinglayer having a low dielectric constant is obtained. Accordingly, therecan be provided a semiconductor device having high reliability and anexcellent transmission speed in a chip circuit.

The resin composition for laminates, provided by the present invention3, is a well-balanced resin composition which has excellent electriccharacteristics of high heat resistance, low dielectric constant and lowdielectric loss tangent and is excellent in moldability. The aboveperformances are further improved by combining the resin composition ofthe present invention with a cyanate ester resin. A laminate ormultilayer printed wiring board using the above resin composition isexcellent in molding at the time of multilayer formation and has highreliability. Further, high-speed processing of a high frequency signaland a low-loss circuit design become possible.

The acrylate compound of the present invention 4 has a high glasstransition temperature and has a low dielectric constant and a lowdielectric loss tangent and is therefore very useful as ahigh-functional high-molecular material. The acrylate compound of thepresent invention 4 can be widely used as a thermally and electricallyexcellent material in various uses such as various coatings, UV coatingcompositions, adhesives, resists and buildup wiring board materials.

The epoxy(meth)acrylate compound of the present invention 5 has a highglass transition temperature and has a low dielectric constant and a lowdielectric loss tangent and is therefore very useful as ahigh-functional high-molecular material. The epoxy(meth)acrylatecompound of the present invention 5 can be widely used as a thermallyand electrically excellent material in various uses such as variouscoatings, UV coating compositions, adhesives, resists and laminates.

It is confirmed that the thermosetting PPE oligomer compound of thepresent invention 6 has the excellent properties (low dielectriccharacteristics, toughness) of PPE, is high in the compatibility with adifferent resin and is to be incorporated into a network in a resinconstitution. Therefore, for example, a varnish for laminates can beeasily prepared and a laminate material excellent in moldingprocessability can be produced. Further, a cured product obtained fromthe oligomer compound alone or a mixture of the oligomer compound and adifferent resin accomplishes low dielectric characteristics and becomesan electric or electronic material having the excellent properties of aPPE polymer. It is found that the use of a compound obtained by adding aphenylene ether structure formed of 2,6-dimethylphenol or2,3,6-trimethylphenol to a bivalent phenol having a cyclic hydrocarbonor an aromatic group, used in the present invention, as raw materialsfor a thermosetting PPE oligomer compound, is more effective atincreasing dielectric characteristics than the use of a compoundobtained by adding a phenylene structure formed of 2,6-dimethylphenol toa bis A type or bis F type phenol. Further, a laminate or multilayerprinted wiring board using the above resin composition of the presentinvention 6 is excellent in molding at the time of multilayer formationand has high reliability. Further, high-speed processing of a highfrequency signal and a low-loss circuit design become possible.

EXAMPLES

The present invention will be explained concretely with reference toExamples, while the present invention shall not be specially limited tothese Examples. In Examples, “part” stands for “part by weight”. Anumber average molecular weight and a weight average molecular weightwere measured according to the gel permeation chromatography (GPC)method. Dielectric constant and dielectric loss tangent were obtained bya cavity resonant oscillation method.

Example 1

Production Process of Bifunctional PPE Oligomer Compound

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 2.7 g (0.012 mol) of CuBr₂, 70.7 g (0.55 mol) ofdi-n-butylamine and 600 g of toluene. The components were stirred at areaction temperature of 40° C. A mixed solution(bivalent phenol of theformula (7): monovalent phenol of the formula (8) in a molar ratio=1:2)obtained by dissolving 59.6 g (0.21 mol) of a bivalent phenol4,4′-(1l-methylethylidene)bis(2,6-dimehtylphenol) and 50.4 g (0.41 mol)of 2,6-dimehtylphenol in 600 g of methanol was dropwise added to thereactor over 120 minutes while carrying out bubbling with 2 L/min ofair. After the completion of the addition, stirring was carried out for30 minutes while continuing the bubbling with 2 L/min of air. A disodiumdihydrogen ethylenediamine tetraacetate aqueous solution was added tothe stirred mixture to terminate the reaction. Then, washing was carriedout with 1N hydrochloric acid aqueous solution and then washing wascarried out with pure water. The thus-obtained solution was concentratedby an evaporator, to remove the methanol. Then, toluene was added toobtain 70% toluene solution. Part of the above toluene solution wasfurther concentrated and then dried under reduced pressure, to obtain apowder. The powder had a number average molecular weight of 690, aweight average molecular weight of 970 and a hydroxyl group equivalentof 360.

Production Process of Epoxy Compound

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 57.1 g (hydroxyl group 0.11mol) of the above toluene solution and 308.4 g of epichlorohydrin. Then,a solution obtained by dissolving 9.1 g (0.13 mol) of sodium ethoxide in32.0 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with pure water, and furthera filtration was carried out, to remove a generated salt and impurities.Excess epichlorohydrin was distilled off from the obtained solution, anddrying under reduced pressure was carried out, to obtain 44.0 g of anepoxy compound. According to the IR analysis of the obtained epoxycompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared, and according to the NMR analysis, a peak derived fromglycidyl ether appeared so that it was confirmed that all functionalgroups were changed.

3 parts of 1-benzyl-2-methylimidazole was added to 100 parts of thethus-obtained epoxy compound. The mixture was molten, degassed andmolded at 150° C. and then cured at 180° C. for 10 hours, to obtain acured product. The cured product had a glass transition temperature of193° C. according to the measurement of dynamic viscoelasticity (DMA).Further, its dielectric constant at 1 GHz was 2.82 and its dielectricloss tangent was 0.0177.

Example 2

Production Process of Bifunctional PPE Oligomer Compound

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 2.7 g (0.012 mol) of CuBr2, 70.7 g (0.55 mol) ofdi-n-butylamine and 600 g of toluene. The components were stirred at areaction temperature of 40° C. A mixed solution(bivalent phenol of theformula (7): monovalent phenols of the formula (8) in a molar ratio=1:2)obtained by dissolving 68.0 g (0.21 mol) of a bivalent phenol4,4′-cyclohexylidenebis[2,6-dimehtylphenol], 25.6 g (0.21 mol) of2,6-dimehtylphenol and 28.6 g (0.21 mol) of 2,3,6-trimethylphenol in 600g of methyl ethyl ketone was dropwise added to the reactor over 120minutes while carrying out bubbling with 2 L/min of air. After thecompletion of the addition, stirring was carried out for 30 minuteswhile continuing the bubbling with 2 L/min of air. A disodium dihydrogenethylenediamine tetraacetate aqueous solution was added to the stirredmixture to terminate the reaction. Then, washing was carried out with 1Nhydrochloric acid aqueous solution and then washing was carried out withpure water. The thus-obtained solution was concentrated by anevaporator, to remove the methyl ethyl ketone. Then, toluene was addedto obtain 70% toluene solution. Part of the above toluene solution wasfurther concentrated and then dried under reduced pressure, to obtain apowder. The powder had a number average molecular weight of 610, aweight average molecular weight of 870 and a hydroxyl group equivalentof 320.

Production Process of Epoxy Compound

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 57.1 g (hydroxyl group 0.13mol) of the above toluene solution and 347.0 g of epichlorohydrin. Then,a solution obtained by dissolving 10.2 g (0.15 mol) of sodium ethoxidein 35.8 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with pure water, and furthera filtration was carried out, to remove a generated salt and impurities.Excess epichlorohydrin was distilled off from the obtained solution, anddrying under reduced pressure was carried out, to obtain 45.2 g of anepoxy compound. According to the IR analysis of the obtained epoxycompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared, and according to the NMR analysis, a peak derived fromglycidyl ether appeared so that it was confirmed that all functionalgroups were changed.

3 parts of 1-benzyl-2-methylimidazole was added to 100 parts of thethus-obtained epoxy compound. The mixture was molten, degassed andmolded at 150° C. and then cured at 180° C. for 10 hours, to obtain acured product. The cured product had a glass transition temperature of192° C. according to the measurement of dynamic viscoelasticity (DMA).Further, its dielectric constant at 1 GHz was 2.80 and its dielectricloss tangent was 0.0175.

Example 3

Production Process of Bifunctional PPE Oligomer Compound

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.3 g (0.013 mol) of CuCl, 79.5 g (0.62 mol) ofdi-n-butylamine and 400 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C. A mixed solution (bivalentphenol of the formula (7): monovalent phenol of the formula (8) in amolar ratio=1:4) obtained by dissolving 42.6 g (0.15 mol) of a bivalentphenol 4,4′-methylenebis(2,3,6-trimehtylphenol) 56.7 g (0.46 mol) of2,6-dimehtylphenol and 21.1 g (0.16 mol) of 2,3,6-trimehtylphenol in 400g of methyl ethyl ketone and 400 g of tetrahydrofuran was dropwise addedto the reactor over 120 minutes while carrying out bubbling with 2 L/minof air. After the completion of the addition, stirring was carried outfor 60 minutes while continuing the bubbling with 2 L/min of air. Adisodium dihydrogen ethylenediamine tetraacetate aqueous solution wasadded to the stirred mixture to terminate the reaction. Then, washingwas carried out with 1N hydrochloric acid aqueous solution and thenwashing was carried out with pure water. The thus-obtained solution wasconcentrated by an evaporator and then dried under reduced pressure, toobtain 113.2 g of an oligomer compound. The oligomer compoundhad anumber average molecular weight of 1,050, a weight average molecularweight of 1,490 and a hydroxyl group equivalent of 550.

Production Process of Epoxy Compound

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 40.0 g (hydroxyl group 0.07mol) of the above oligomer compound and 336.5 g of epichlorohydrin.Then, a solution obtained by dissolving 5.9 g (0.09 mol) of sodiumethoxide in 20.8 g of ethanol was dropwise added from the droppingfunnel over 60 minutes. After the completion of the addition, stirringwas carried out for 5 hours. Then, washing was carried out with purewater, and further a filtration was carried out, to remove a generatedsalt and impurities. Excess epichlorohydrin was distilled off from theobtained solution, and drying under reduced pressure was carried out, toobtain 42.8 g of an epoxy compound. According to the IR analysis of theobtained epoxy compound, the absorption peak (3,600 cm-1) of a phenolichydroxyl group disappeared, and according to the NMR analysis, a peakderived from glycidyl ether appeared so that it was confirmed that allfunctional groups were changed.

3 parts of 1-benzyl-2-methylimidazole was added to 100 parts of thethus-obtained epoxy compound. The mixture was molten, degassed andmolded at 150° C. and then cured at 180° C. for 10 hours, to obtain acured product. The cured product had a glass transition temperature of198° C. according to the measurement of dynamic viscoelasticity (DMA).Further, its dielectric constant at 1 GHz was 2.79 and its dielectricloss tangent was 0.0173.

Example 4

Production Process of Bifunctional PPE Oligomer Compound

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.1 g (0.11 mol) of CuCl, 66.3 g (0.51 mol) ofdi-n-butylamine and 400 g of toluene. The components were stirred at areaction temperature of 40° C. A mixed solution (bivalent phenol of theformula (7): monovalent phenol of the formula (8) in a molar ratio=1:8)obtained by dissolving 33.1 g (0.077 mol) of a bivalent phenol4,4′-[1,4-phenylenebis(1-methylethylidene)]bis(2,3,6-trimehtylphenol)and 75.6 g (0.62 mol) of 2,6-dimehtylphenol in 400 g of methyl ethylketone and 400 g of tetrahydrofuran was dropwise added to the reactorover 120 minutes while carrying out bubbling with 2 L/min of air. Afterthe completion of the addition, stirring was carried out for 30 minuteswhile continuing the bubbling with 2 L/min of air. A disodium dihydrogenethylenediamine tetraacetate aqueous solution was added to the stirredmixture to terminate the reaction. Then, washing was carried out with 1Nhydrochloric acid aqueous solution and then washing was carried out withpure water. The thus-obtained solution was concentrated by an evaporatorand then dried under reduced pressure, to obtain 102.2 g of an oligomercompound. The oligomer compoundhad a number average molecular weight of1,820, a weight average molecular weight of 2,510 and a hydroxyl groupequivalent of 970.

Production Process of Epoxy Compound

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 40 g (hydroxyl group 0.04 mol)of the above oligomer compound and 267.1 g of epichlorohydrin. Then, asolution obtained by dissolving 3.4 g (0.05 mol) of sodium ethoxide in11.8 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with pure water, and furthera filtration was carried out, to remove a generated salt and impurities.Excess epichlorohydrin was distilled off from the obtained solution, anddrying under reduced pressure was carried out, to obtain 41.1 g of anepoxy compound. According to the IR analysis of the obtained epoxycompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared, and according to the NMR analysis, a peak derived fromglycidyl ether appeared so that it was confirmed that all functionalgroups were changed.

3 parts of 1-benzyl-2-methylimidazole was added to 100 parts of thethus-obtained epoxy compound. The mixture was molten, degassed andmolded at 150° C. and then cured at 18° C. for 10 hours, to obtain acured product. The cured product had a glass transition temperature of197° C. according to the measurement of dynamic viscoelasticity (DMA).Further, its dielectric constant at 1 GHz was 2.81 and its dielectricloss tangent was 0.0168.

Example 5

Production Process of Bifunctional PPE Oligomer Compound

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 2.7 g (0.012 mol) of CuBr₂, 70.7 g (0.55 mol) ofdi-n-butylamine and 600 g of toluene. The components were stirred at areaction temperature of 40° C. A mixed solution(bivalent phenol of theformula (7): monovalent phenol of the formula (8) in a molar ratio=1:2)obtained by dissolving 53.8 g (0.21 mol) of a bivalent phenol4,4′-methylenebis(2,6-dimehtylphenol) and 50.4 g (0.41 mol) of2,6-dimehtylphenol in 600 g of methanol was dropwise added to thereactor over 120 minutes while carrying out bubbling with 2 L/min ofair. After the completion of the addition, stirring was carried out for30 minutes while continuing the bubbling with 2 L/min of air. A disodiumdihydrogen ethylenediamine tetraacetate aqueous solution was added tothe stirred mixture to terminate the reaction. Then, washing was carriedout with 1N hydrochloric acid aqueous solution and then washing wascarried out with pure water. The thus-obtained solution was concentratedby an evaporator and then dried under reduced pressure, to obtain 97.9 gof an oligomer compound. The oligomer compound had a number averagemolecular weight of 620, a weight average molecular weight of 860 and ahydroxyl group equivalent of 320.

Production Process of Allyl Compound

A solution obtained by dissolving 50.0 g (hydroxyl group 0.16 mol) ofthe above oligomer compound and 37.8 g (0.31 mol) of allyl bromide in150 g of methylene chloride, and 120 ml of 1N sodium hydroxide aqueoussolution were placed in a reactor equipped with a stirrer and athermometer at room temperature. Further, 5.6 g (0.02 mol) ofbenzyltri-n-butylammonium bromide as a phase transfer catalyst was addedto the reactor. The mixture was stirred for 5 hours. Then, washing wascarried out with 0.1N hydrochloric acid aqueous solution, then washingwas carried out with pure water, and further a filtration was carriedout, to remove a generated salt and impurities. The methylene chloridewas distilled off from the obtained solution, and drying under reducedpressure was carried out, to obtain 54.15 g of an allyl compound.According to the IR analysis of the obtained allyl compound, theabsorption peak (3,600cm-1) of a phenolic hydroxyl group disappeared,and according to the NMR analysis, a peak derived from an allyl groupappeared so that it was confirmed that all functional groups werechanged.

The allyl compound was molten, degassed and molded at 150° C. and thencured at 230° C. for 3 hours, to obtain a cured product. The curedproduct had a glass transition temperature of 208° C. according to themeasurement of dynamic viscoelasticity (DMA). Further, its dielectricconstant at 1 GHz was 2.76 and its dielectric loss tangent was 0.0046.

Comparative Example 1

3 parts of 1-benzyl-2-methylimidazole was added to 100 parts of3,3′,5,5′-tetramethyl-[1,1′-biphenyl]-4,4′-glycidyl ether which was abiphenyl type epoxy resin for a semiconductor-sealing material. Themixture was molten, degassed and molded at 150° C. and then cured at180° C. for 10 hours, to obtain a cured product. The cured product had aglass transition temperature of 133° C. according to the measurement ofdynamic viscoelasticity (DMA). Further, its dielectric constant at 1 GHzwas 3.06 and its dielectric loss tangent was 0.030.

Comparative Example 2

3 parts of 1-benzyl-2-methylimidazole was added to 100 parts ofdicyclopentadiene type epoxy for a semiconductor-sealing material. Themixture was molten, degassed and molded at 150° C. and then cured at180° C. for 10 hours, to obtain a cured product. The cured product had aglass transition temperature of 182° C. according to the measurement ofdynamic viscoelasticity (DMA). Further, its dielectric constant at 1 GHzwas 2.90 and its dielectric loss tangent was 0.020.

Table 1 shows the above results. TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5CEx. 1 CEx. 2 dielectric 2.82 2.80 2.79 2.75 2.76 3.06 2.90 constant (1GHz) dielectric 0.0177 0.0175 0.0173 0.0140 0.0046 0.0303 0.0204 losstangent (1 GHz) Tg(DMA)/° C. 193 192 198 197 208 133 182Ex. = Example, CEx. = Comparative Example

Referential Example 1 Production Process of Bifunctional OPE-2Ep (1)

(Production Process of Bifunctional OPE)

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.3 g (0.013 mol) of CuCl, 79.5 g (0.62 mol) ofdi-n-butylamine and 600 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C. A mixed solution (bivalentphenol:monovalent phenols in a molar ratio=1:4) obtained by dissolving42.6 g (0.15 mol) of 4,4′-(1-methylethylidene)bis(2,6-dimehtylphenol),56.7 g (0.46 mol) of 2,6-dimehtylphenol and 21.1 g (0.16 mol) of2,3,6-trimethylphenol in 600 g of methyl ethyl ketone was dropwise addedto the reactor over 120 minutes while carrying out bubbling with 2 L/minof air. After the completion of the addition, stirring was carried outfor 30 minutes while continuing the bubbling with 2 L/min of air. Adisodium dihydrogen ethylenediamine tetraacetate aqueous solution wasadded to the stirred mixture to terminate the reaction. Then, washingwas carried out with 1N hydrochloric acid aqueous solution and thenwashing was carried out with pure water. The thus-obtained solution wasconcentrated by an evaporator and then dried under reduced pressure, toobtain 112.3 g of a bifunctional OPE. The bifunctional OPE was measuredaccording to the gel permeation chromatography (GPC) method. As a resultthereof, the bifunctional OPE had a number average molecular weight of1,080. Further, it had a hydroxyl group equivalent of 550.

(Production Process of Bifunctional OPE-2Ep)

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 40.0 g (hydroxyl group: 0.073mol) of the above bifunctional OPE and 201.9 g of epichlorohydrin. Then,a solution obtained by dissolving 5.9 g (0.087 mol) of sodium ethoxidein 20.8 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with pure water, and furthera filtration was carried out, to remove a generated salt and impurities.Excess epichlorohydrin was distilled off from the obtained solution, anddrying under reduced pressure was carried out, to obtain 42.4 g of abifunctional OPE-2Ep (number average molecular weight: 1,230, to bereferred to as “bifunctional OPE-2Ep [A]” hereinafter). According to theIR analysis of the obtained bifunctional OPE-2Ep [A], the absorptionpeak (3,600 cm−1) of a phenolic hydroxyl group disappeared and,according to the NMR analysis, a peak derived from glycidyl etherappeared so that it was confirmed that all functional groups werechanged.

Referential Example 2 Production Process of Bifunctional OPE-2Ep (2)

(Production Process of Bifunctional OPE)

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 2.7 g (0.012 mol) of CuBr₂, 66.3 g (0.51 mol) ofdi-n-butylamine and 500 g of toluene. The components were stirred at areaction temperature of 40° C. A mixed solution (bivalentphenol:monovalent phenol in a molar ratio=1:8) obtained by dissolving21.9 g (0.077 mol) of 4,4′-(1-methylethylidene)bis(2,6-dimehtylphenol)and 75.6 g (0.62 mol) of 2,6-dimehtylphenol in 600 g of methanol wasdropwise added to the reactor over 120 minutes while carrying outbubbling with 2 L/min of air. After the completion of the addition,stirring was carried out for 30 minutes while continuing the bubblingwith 2 L/min of air. A disodium dihydrogen ethylenediamine tetraacetateaqueous solution was added to the stirred mixture to terminate thereaction. Then, washing was carried out with 1N hydrochloric acidaqueous solution and then washing was carried out with pure water. Thethus-obtained solution was concentrated by an evaporator to obtain a 70%toluene solution of a bifunctional OPE. Part of the above toluenesolution was further concentrated and then dried under reduced pressure,to obtain a powder. According to the same measurement as that in theReferential Example 1, the powder had a number average molecular weightof 1,670. Further, it had a hydroxyl group equivalent of 830.

(Production Process of Bifunctional OPE-2Ep)

41.0 g of a bifunctional OPE-2Ep (number average molecular weight:1,820, to be referred to as “bifunctional OPE-2Ep [B]” hereinafter) wasobtained in the same manner as in Referential Example 1 except that 57.1g (hydroxyl group: 0.048 mol) of the above-obtained bifunctional OPEtoluene solution, 223.0 g of epichlorohydrin, 13.8 g of ethanol and 3.9g (0.058 mol) of sodium ethoxide were used. According to the same methodas that in Referential Example 1, it was confirmed that all functionalgroups were changed.

Referential Example 3 Production Process of Bifunctional OPE-2Ep (3)

(Production Process of Bifunctional OPE)

A 70% toluene solution of a bifunctional OPE was obtained in the samemanner as in Referential Example 2 except that there was used a mixedsolution (bivalent phenol:monovalent phenol in a molar ratio=1:15)obtained by dissolving 12.5 g (0.044 mol) of4,4′-(1-methylethylidene)bis(2,6-dimehtylphenol) and 79.9 g (0.66 mol)of 2,6-dimehtylphenol in 600 g of methanol. Part of the solution wasfurther concentrated and then dried under reduced pressure to obtain apowder. The powder had a number average molecular weight of 3,350 and ahydroxyl group equivalent of 1,670. The number average molecular weightwas measured in the same manner as in Referential Example 1.

(Process for the Production of Bifunctional OPE-2Ep)

49.6 g of a bifunctional OPE-2Ep (number average molecular weight:3,520, to be referred to as “bifunctional OPE-2Ep [C]” hereinafter) wasobtained in the same manner as in Referential Example 1 except that 71.4g (hydroxyl group: 0.030 mol) of the above-obtained bifunctional OPEtoluene solution, 193.9 g of epichlorohydrin, 8.6 g of ethanol and 2.4 g(0.036 mol) of sodium ethoxide were used. According to the same methodas that in Referential Example 1, it was confirmed that all functionalgroups were changed.

Referential Example 4 Production Process of an Epoxy-ModifiedPolyphenylene Ether Resin

47.7 g of an epoxy-modified polyphenylene ether resin (to be referred toas “epoxy-modified PPE resin” hereinafter, number average molecularweight: 16,000) was obtained in the same manner as in ReferentialExample 1 except that 50 g of a commercially available polyphenyleneether resin (supplied by Mitsubishi Gas Chemical Co., Inc., numberaverage molecular weight: 16,000, hydroxyl group: 0.003 mol), 200 g oftoluene, 2.9 g of epichlorohydrin, 2.2 g of ethanol and 0.6 g (0.009mol) of sodium ethoxide were used. According to the same method as thatin Referential Example 1, it was confirmed that 95% of functional groupswere changed.

Example 6

There were used 32.40 parts (7.02% by weight) of YX400H (supplied byJapan Epoxy Resins Co., Ltd, epoxy equivalent 195) as a biphenyl typeepoxy resin, 10.80 parts (2.34% by weight) of 195XL (supplied bySumitomo Chemical Co., Ltd., epoxy equivalent 195) as a cresol novolaktype epoxy resin, 3.78 parts (0.82% by weight) of EBS400T (supplied bySumitomo Chemical Co., Ltd., epoxy equivalent 400) as a flame-retardantbisphenol type epoxy resin, 11.50 parts (2.49% by weight) ofbifunctional OPE-2Ep [B], 15.93 parts (3.45% by weight) of KAYAHARD NHN(supplied by Nippon Kayaku Co., Ltd., hydroxyl group equivalent 140) asa naphthalene type phenol resin composition, 15.93 parts (3.45% byweight) of MILEX 225-3L (supplied by Mitsui Chemicals, Inc., hydroxylequivalent 173) as a P-xylylene-phenol compolymer, a powder obtained bytreating 360.50 parts (78.08% by weight) of a fused silica powder with2.13 parts (0.46% by weight) of γ-glycidoxypropyltrimethoxysilane, 0.95part (0.21% by weight) of triphenylphosphine, 1.36 parts (0.30% byweight) of natural carnauba, 0.99 parts (0.21% by weight) of carbonblack and 5.40 parts (1.17% by weight) of antimony trioxide. First, thebifunctional OPE-2Ep[B] and the epoxy resins were dissolved in thetoluene, to obtain a homogenous toluene solution having a concentrationof 30% by weight. The toluene was removed from the above toluenesolution, to obtain a mixture of the epoxy resins and the bifunctionalOPE-2Ep. The above materials were added to the mixture and the resultantmixture was kneaded with a heating roller at 85° C. for approximately 5minutes. Then, the kneaded mixture was pulverized so as to have adiameter of approximately 5 mm, whereby a sealing epoxy resincomposition was obtained.

Examples 7 to 9 and Comparative Examples 3 to 5

Sealing epoxy resin compositions were obtained in the same manner as inExample 6 except that materials were mixed in amount ratios shown inTable 2. The obtained sealing epoxy resin compositions of Examples 6 to9 and Comparative Examples 3 to 5 were subjected to a test of heatresistance against soldering, and these resin compositions wereevaluated for dielectric constant. Further, the resin compositions weremeasured for melt viscosity, cured products thereof were measured forbending strength, and the resin compositions were measured formoldability when used for sealing.

The above moldability test and the test of heat resistance againstsoldering were carried out under the following conditions. Asemiconductor chip having 7.6 mm×7.6 mm×0.4 mm (thickness) was mountedon an alloy lead frame having a die pad size of 8.2 mm×8.2 mm with asilver paste, and molding was carried out by using a 60-pin flat packagemolding die having an outside dimension of 19 mm×15 mm×1.8 mm(thickness) to prepare a test specimen. The obtained test specimen waschecked for existence or nonexistence of voids in a sealing layer withan ultrasonic exploratory device. When no voids existed, moldability wasgood (expressed by O). When voids existed, moldability was poor(expressed by X). Further, five test specimens were prepared in theabove manner. Each of the test specimens was allowed to absorb moistureat 85° C. at 85% RH for 72 hours, then it was immersed in a solderhaving a temperature of 260° C. for 10 seconds. The procedures ofabsorption and immersion were carried out two times. After thesoldering, the sealing layer was checked for existence or nonexistenceof cracks with an ultrasonic exploratory device and the sealing layerhaving cracks was considered to be defective.

The above dielectric constant was measured by using the above specimenon the basis of the measurement method of a molded article according toJIS-K-6911.

The above bending strength of cured product was measured as follows. Oneof the sealing epoxy resin compositions was cured to prepare a testspecimen having a size of 10 mm×4 mm×100 mm, the test specimen wasmeasured for three-point bending strength at room temperature and at240° C. under conditions of distance between supports=64 mm and acrosshead speed=2 mm/min.

The above melt viscosity of the resin composition was measured at 175°C. with an elevated type flow tester.

Table 3 shows the above results. It is confirmed that, when bifunctionalOPE-2Eps having a number average molecular weight of 700 to 3,000 areused, moldability is good, no voids occur, dieletric constant is low,bending strength at high temperatures is excellent and melt viscosity islow. TABLE 2 (Unit: % by weight) CEx. CEx. Ex. 6 Ex. 7 Ex. 8 Ex. 9 3CEx. 4 5 Epoxy YX4000H 7.02 6.06 9.36 7.02 7.02 7.02 8.87 resin 195XL2.34 2.34 2.34 2.34 2.98 EBS400T 0.82 0.82 0.82 0.82 0.82 0.82 0.82Bifunctional 2.49 OPE-2Ep [A] Bifunctional 2.49 5.79 2.49 OPE-2Ep [B]Bifunctional 2.49 OPE-2Ep [C] Epoxy-modified 2.49 PPE KAYAHARD NHN 3.453.45 3.45 3.45 3.45 3.45 3.45 MILEX 225-3L 3.45 3.45 3.45 3.45 3.45 3.453.45 Fused silica 78.08 78.08 78.08 78.08 78.08 78.08 78.08 powderCoupling agent 0.46 0.46 0.46 0.46 0.46 0.46 0.46 Triphenyl 0.21 0.210.21 0.21 0.21 0.21 0.21 phosphine Natural 0.30 0.30 0.30 0.30 0.30 0.300.30 carnauba Carbon black 0.21 0.21 0.21 0.21 0.21 0.21 0.21 antimony1.17 1.17 1.17 1.17 1.17 1.17 1.17 trioxideEx. = Example, CEx. = Comparative Example

TABLE 3 CEx. CEx. CEx. Ex. 6 Ex. 7 Ex. 8 Ex. 9 3 4 5 Number of the 0/50/5 0/5 0/5 2/5 5/5 5/5 occurrence of cracks after soldering Number ofdefectives/ Number of specimens tested dielectric 4.7 4.2 4.7 4.7 4.74.4 5.1 constant Moldability ◯ ◯ ◯ ◯ ◯ X ◯ Bending Room 154 159 155 154145 148 144 strength temperature (MPa) 240° C. 12.5 13.5 12.4 11.5 7.58.8 5.9 Melt viscosity 29 33 22 24 37 94 20 (Pa · s)Ex. = Example, CEx. = Comparative Example

Example 10

70 parts of the same bifunctional OPE-2Ep as that obtained inReferential Example 1, 20 parts of tetrabromobisphenol A epoxy (suppliedby Dainippon Ink And Chemicals, Incorporated, trade name: EPICLON-153),10 parts of 4,4′-diaminodiphenylmethane and 0.07 part of2-methylimidazole were dissolved in methyl ethyl ketone, to prepare avarnish having a resin content of 60% by weight.

A glass cloth (NE glass product: trade name WEX983, supplied by NittoBoseki Co., Ltd.) was impregnated with the above varnish, and then itwas treated with a hot-air dryer, to obtain B-stage prepreg. Eightsheets of the prepreg and a copper foil (thickness: 18 μm, supplied byMitsui Mining & smelting Co., Ltd., trade name: 3EC-3) were laminatedand these materials were hot-pressed at 200° C. in vacuum for 2 hours toobtain a 0.8 mm-thick copper-clad laminate. Table 5 shows the physicalproperties of the copper-clad laminate.

Example 11 and Comparative Example 6-8

Copper-clad laminates were obtained in the same manner as in Example 10except that thermosetting resins were mixed in amount ratios shown inTable 4. In Comparative Example 7, toluene was used as a solvent, sincean ingredient was insoluble in methyl ethyl ketone. TABLE 4 Ex. 10 Ex.11 CEx. 6 CEx. 7 CEx. 8 Bifunctional 70 50 — — — OPE-2Ep General-purposePPE — — — 30 — polymer Bisphenol A type — 30 — 30 30 cyanate prepolymer4,4′dimethyl 10 — 18 — — diphenylmethane Tetrabromobisphenol 20 20 20 2020 A epoxy Bisphenol A epoxy — — 10 20 — Phenol novolak type — — 52 — 50epoxy iron — 0.04 — 0.04 0.04 acetylacetonate 2-methylimidazole 0.07 —0.07 — —Ex. = Example, CEx. = Comparative Example

General-purpose PPE polymer: supplied by Mitsubishi Gas Chemical Co.,Inc., number average molecular weight: 24,000.

Bisphenol A type cyanate prepolymer: prepolymer of2,2-bis(4-cyanatophenyl)propane.

Tetrabromobisphenol A epoxy: EPICLON-153, supplied by Dainippon Ink AndChemicals, Incorporated.

Bisphenol A epoxy: DER-331L, supplied by Dow Chemical Japan Ltd.

Phenol novolak type epoxy: EPPN-201, supplied by Nippon Kayaku Co., Ltd.TABLE 5 Ex. 10 Ex. 11 CEx. 6 CEx. 7 CEx. 8 Grass transition 184° C. 213°C. 156° C. 202° C. 190° C. temperature (DMA method) Dielectric 3.5 3.54.2 3.5 4.0 constant (1 GHz) Dielectric loss 0.0087 0.0052 0.021 0.00460.014 tangent (1 GHz) Copper-foil peeling 1.4 1.2 1.4 1.2 0.9 strength(kN/m) Moldability ◯ ◯ ◯ X ◯ Heat resistance against soldering aftermoisture absorption (number of swelling/number of tested specimens) 1hour treatment 0/3 0/3 0/3 2/3 0/3 2 hours treatment 0/3 0/3 0/3 3/3 0/33 hours treatment 0/3 0/3 2/3 3/3 1/3Ex. = Example, CEx. = Comparative Example

In Examples and Comparative Examples, measurements were carried out bythe following devices and methods.

-   -   Grass transition temperature (Tg): Obtained by a loss tangent        (tan δ) peak of a dynamic viscoelasticity measurement.    -   Dielectric constant and dielectric loss tangent: Measured        according to a cavity resonant oscillation method.    -   Copper foil peeling strength: Peeling strength of a copper foil        having a width of 10 mm in a 90-degree direction was measured        according to JIS C6481.    -   Heat resistance against soldering after moisture absorption: A        sample was prepared by removing the entire copper foil, the        sample was treated for absorption under PCT conditions at        121° C. at 0.2 MPa for 1 to 3 hours and then the sample was        immersed in a solder bath at 260° C. for 30 seconds. The sample        was visually observed for the occurrence of a delamination        (swelling).    -   Moldability: Determined depending upon whether or not an        internal layer pattern of a 70 μm-thick copper foil could be        embedded without voids.

Example 12

(Synthesis of Bifunctional PPE Oligomer Compound)

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) ofdi-n-butylamine and 400 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C. A solution obtained bydissolving 45.4 g (0.16 mol) of a bivalent phenol4,4′-(1-methylethylidene)bis(2,6-dimehtylphenol) and 58.6 g (0.48 mol)of 2,6-dimehtylphenol in 800 g of methyl ethyl ketone was dropwise addedto the reactor over 120 minutes while carrying out bubbling with 2 L/minof air. After the completion of the addition, stirring was carried outfor 60 minutes while continuing the bubbling with 2 L/min of air. Adisodium dihydrogen ethylenediamine tetraacetate aqueous solution wasadded to the reaction mixture to terminate the reaction. Then, washingwas carried out with 1N hydrochloric acid aqueous solution and thenwashing was carried out with pure water. The thus-obtained solution wasconcentrated by an evaporator and then dried under reduced pressure, toobtain 98.8 g of an oligomer compound. The oligomer compound had anumber average molecular weight of 845, a weight average molecularweight of 1,106 and a hydroxyl group equivalent of 451.

(Introduction of Z-Site)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 50 g (hydroxyl group 0.11 mol) of the above oligomercompound, 15.3 g of potassium carbonate and 400 ml of acetone and themixture was refluxed under nitrogen for 3 hours. Then, 22.1 g of6-bromo-1-hexanol was dropwise added to the mixture over 1 hour. Afterthe completion of the addition, the resultant mixture was furtherrefluxed for 30 hours. After neutralization with hydrochloric acid, alarge amount of pure water was added to the mixture to obtain aprecipitate, and toluene was added to perform extraction. The obtainedsolution was concentrated by evaporator, and the concentrated solutionwas dropwise added to methanol to obtain a precipitate again. A solidwas recovered by filtration. Then, drying under reduced pressure wascarried out to obtain 55.2 g of a resin. The resin had a number averagemolecular weight of 1,049 a weight average molecular weight of 1,398 anda hydroxyl group equivalent of 554.

(Synthesis of an Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 30 g of the above resin, 4.7 g of an acrylic acid, 30 g oftoluene, 0.12 g of p-toluenesulfonic acid and 0.03 g of hydroquinone.The mixture was allowed to react under heat with refluxing. A generationwater was quantified and collected with a water quantitative receiver.At the time when 0.9 g of the generation water was collected, thereaction mixture was cooled. The reaction temperature was 110 to 120° C.The reaction mixture was neutralized with 20% NaOH aqueous solution andthen washed with 20% NaCl aqueous solution. The solvent was evaporatedunder a reduced pressure, to obtain 29.6 g of an acrylate compound. Theacrylate compound had a number average molecular weight of 1,201 and aweight average molecular weight of 1,611. 10 g of the above resin wasmolten, degassed and molded at 150° C. and then cured at 200° C. for 6hours, to obtain a cured product.

6 g of the above acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface by a screen printing machine, and thendried with an air dryer at 80° C. for 60 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at1,500 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was B.

Example 13

(Synthesis of Bifunctional PPE Oligomer Compound)

102.6 g of an oligomer compound was obtained in the same manner as inExample 12 except that, in the synthesis of bifunctional PPE oligomercompound in Example 12, the dropwise addition solution was replaced witha solution obtained by dissolving 51.8 g (0.16 mol) of a bivalent phenol4,4′-cyclohexylidenebis(2,6-dimethylphenol) and 58.6 g (0.48 mol) of2,6-dimethylphenol in 800 g of methyl ethyl ketone. The oligomercompound had a number average molecular weight of 877, a weight averagemolecular weight of 1,183 and a hydroxyl group equivalent of 477.

(Introduction of Z-Site)

An airtight reactor was charged with 50 g of the above oligomercompound, and 20 g of toluene and 1 g of potassium hydroxide as acatalyst were added to the reactor. The inside atmosphere of the reactorwas substituted with a nitrogen gas. Then, the mixture was heated withstirring, and at the time when the inside temperature reached 70° C. 5.1g of ethylene oxide was press-injected to the mixture. The resultantmixture was further heated up to 100° C. and an addition reaction wascarried out at 100° C. for 4 hours. Further, the reaction mixture wasaged for 1 hour. A reaction product was neutralized with hydrochloricacid and then washed with pure water. The solvent was evaporated under areduced pressure, to obtain 49.2 g of a resin having Z-sites introducedtherein. The above resin having Z-sites introduced therein had a numberaverage molecular weight of 984, a weight average molecular weight of1,297 and a hydroxyl group equivalent of 522.

(Synthesis of an Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 30 g of the above resin having z-sites introduced therein,5.0 g of an acrylic acid, 30 g of toluene, 0.13 g of p-toluenesulfonicacid and 0.03 g of hydroquinone. The mixture was allowed to react underheat with refluxing. A generation water was quantified and collectedwith a water quantitative receiver. At the time when 1.0 g of thegeneration water was collected, the reaction mixture was cooled. Thereaction temperature was 110 to 120° C. The reaction mixture wasneutralized with 20% NaOH aqueous solution and then washed with 20% NaClaqueous solution. The solvent was evaporated under a reduced pressure,to obtain 29.8 g of an acrylate compound. The acrylate compound had anumber average molecular weight of 1,087 and a weight average molecularweight of 1,421. 10 g of the above acrylate compound was molten,degassed and molded at 150° C. and then cured at 200° C. for 6 hours, toobtain a cured product.

6 g of the above acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface by a screen printing machine, and thendried with an air dryer at 80° C. for 60 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at1,500 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was B.

Example 14 (Synthesis of Bifunctional PPE Oligomer Compound)

97.4 g of an oligomer compound was obtained in the same manner as inExample 12 except that, in the synthesis of bifunctional PPE oligomercompound in Example 12, the dropwise addition solution was replaced witha solution obtained by dissolving 45.4 g (0.16 mol) of a bivalent phenol4,4′-methylidenebis(2,3,6-trimethylphenol) and 58.6 g (0.48 mol) of2,6-dimethylphenol in 800 g of methyl ethyl ketone. The oligomercompound had a number average molecular weight of 852, a weight averagemolecular weight of 1,133 and a hydroxyl group equivalent of 460.

(Introduction of Z-Site)

An airtight reactor was charged with 50 g of the above oligomercompound, and 20 g of toluene and 1 g of potassium hydroxide as acatalyst were added to the reactor. The inside atmosphere of the reactorwas substituted with a nitrogen gas. Then, the mixture was heated withstirring, and at the time when the inside temperature reached 70° C. 5.3g of ethylene oxide was press-injected to the mixture. The resultantmixture was further heated up to 100° C. and an addition reaction wascarried out at 100° C. for 4 hours. Further, the reaction mixture wasaged for 1 hour. A reaction product was neutralized with hydrochloricacid and then washed with pure water. The solvent was evaporated under areduced pressure, to obtain 49.3 g of an oligomer compound havingZ-sites introduced therein. The above oligomer compound had a numberaverage molecular weight of 951, a weight average molecular weight of1,241 and a hydroxyl group equivalent of 506.

(Synthesis of an Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 30 g of the above oligomer compound, 5.2 g of an acrylicacid, 30 g of toluene, 0.13 g of p-toluenesulfonic acid and 0.03 g ofhydroquinone. The mixture was allowed to react under heat withrefluxing. A generation water was quantified and collected with a waterquantitative receiver. At the time when 1.1 g of the generation waterwas collected, the reaction mixture was cooled. The reaction temperaturewas 110 to 120° C. The reaction mixture was neutralized with 20% NaOHaqueous solution and then washed with 20% NaCl aqueous solution. Thesolvent was evaporated under a reduced pressure, to obtain 29.9 g of anacrylate compound. The acrylate compound had a number average molecularweight of 1,078 and a weight average molecular weight of 1,409. 10 g ofthe above acrylate compound was molten, degassed and molded at 150° C.and then cured at 200° C. for 6 hours, to obtain a cured product.

6 g of the above acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface by a screen printing machine, and thendried with an air dryer at 80° C. for 60 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at1,500 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was B.

Example 15

(Synthesis of Bifunctional PPE Oligomer Compound)

114.6 g of an oligomer compound was obtained in the same manner as inExample 12 except that, in the synthesis of bifunctional PPE oligomercompound in Example 12, the dropwise addition solution was replaced witha solution obtained by dissolving 68.8 g (0.16 mol) of a bivalent phenol4,4′-[1,4-phenylenebis(1-methylethylidene)]bis(2,3,6-trime thylphenol)and 58.6 g (0.48 mol) of 2,6-dimethylphenol in 800 g of methyl ethylketone. The oligomer compound had a number average molecular weight of934, a weight average molecular weight of 1,223 and a hydroxyl groupequivalent of 496.

(Introduction of Z-Site)

An airtight reactor was charged with 50 g of the above oligomercompound, and 25 g of toluene and 1 g of potassium hydroxide as acatalyst were added to the reactor. The inside atmosphere of the reactorwas substituted with a nitrogen gas. Then, the mixture was heated withstirring, and at the time when the inside temperature reached 70° C. 6.4g of propylene oxide was press-injected to the mixture. The resultantmixture was further heated up to 100° C. and an addition reaction wascarried out at 100° C. for 4 hours. Further, the reaction mixture wasaged for 1 hour. A reaction product was neutralized with hydrochloricacid and then washed with pure water. The solvent was evaporated under areduced pressure, to obtain 50.3 g of an oligomer compound havingZ-sites introduced therein. The above resin having Z-sites introducedtherein had a number average molecular weight of 1,068, a weight averagemolecular weight of 1,391 and a hydroxyl group equivalent of 553.

(Synthesis of an Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 30 g of the above oligomer compound having z-sitesintroduced therein, 4.7 g of an acrylic acid, 30 g of toluene, 0.13 g ofp-toluenesulfonic acid and 0.03 g of hydroquinone. The mixture wasallowed to react under heat with refluxing. A generation water wasquantified and collected with a water quantitative receiver. At the timewhen 1.0 g of the generation water was collected, the reaction mixturewas cooled. The reaction temperature was 110 to 120° C. The reactionmixture was neutralized with 20% NaOH aqueous solution and then washedwith 20% NaCl aqueous solution three times. The solvent was evaporatedunder a reduced pressure, to obtain 29.6 g of an acrylate compound. Theacrylate compound had a number average molecular weight of 1,210 and aweight average molecular weight of 1,588. 10 g of the above acrylatecompound was molten, degassed and molded at 150° C. and then cured at200° C. for 6 hours, to obtain a cured product.

6 g of the above acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface by a screen printing machine, and thendried with an air dryer at 80° C. for 60 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at1,500 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was B.

Example 16

(Synthesis of Bifunctional PPE Oligomer Compound)

94.6 g of an oligomer compound was obtained in the same manner as inExample 12 except that, in the synthesis of bifunctional PPE oligomercompound in Example 12, the dropwise addition solution was replaced witha solution obtained by dissolving 41.0 g (0.16 mol) of a bivalent phenol4,4′-methylenebis(2,6-dimethylphenol) and 58.6 g (0.48 mol) of2,6-dimethylphenol in 800 g of methyl ethyl ketone. The oligomercompound had a number average molecular weight of 801, a weight averagemolecular weight of 1,081 and a hydroxyl group equivalent of 455.

(Introduction of Z-Site)

An airtight reactor was charged with 50 g of the above oligomercompound, and 25 g of toluene and 1 g of potassium hydroxide as acatalyst were added to the reactor. The inside atmosphere of the reactorwas substituted with a nitrogen gas. Then, the mixture was heated withstirring, and at the time when the inside temperature reached 70° C. 7.0g of propylene oxide was press-injected to the mixture. The resultantmixture was further heated up to 100° C. and an addition reaction wascarried out at 100° C. for 4 hours. Further, the reaction mixture wasaged for 1 hour. A reaction product was neutralized with hydrochloricacid and then washed with pure water. The solvent was evaporated under areduced pressure, to obtain 50.7 g of an oligomer compound havingZ-sites introduced therein. The above resin having Z-sites introducedtherein had a number average molecular weight of 935, a weight averagemolecular weight of 1,232 and a hydroxyl group equivalent of 510.

(Synthesis of an Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 30 g of the above oligomer compound having z-sitesintroduced therein, 5.1 g of an acrylic acid, 30 g of toluene, 0.13 g ofp-toluenesulfonic acid and 0.03 g of hydroquinone. The mixture wasallowed to react under heat with refluxing. A generation water wasquantified and collected with a water quantitative receiver. At the timewhen 1.1 g of the generation water was collected, the reaction mixturewas cooled. The reaction temperature was 110 to 120° C. The reactionmixture was neutralized with 20% NaOH aqueous solution and then washedwith 20% NaCl aqueous solution. The solvent was evaporated under areduced pressure, to obtain 29.8 g of an acrylate compound. The acrylatecompound had a number average molecular weight of 1,048 and a weightaverage molecular weight of 1,408. 10 g of the above acrylate compoundwas molten, degassed and molded at 150° C. and then cured at 200° C. for6 hours, to obtain a cured product.

6 g of the above acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface by a screen printing machine, and thendried with an air dryer at 80° C. for 60 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at1,500 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was B.

Comparative Example 9

10 g of bisphenol A ethylene oxide adduct diacrylate (LIGHT-ACRYLATEBP-4EA, suppllied by KYOEISHA CHEMICAL Co., LTD.) was degassed andmolded at 100° C. and then cured at 200° C. for 6 hours, to obtain acured product.

The cured products obtained in Examples 12-16 and Comparative Example 9were evaluated for properties by the following methods.

Grass transition temperature (Tg): Obtained by a dynamic viscoelasticitymeasurement (DMA). Measurements were carried out at an oscillationfrequency of 10 Hz.

Dielectric constant and dielectric loss tangent: Measured according to acavity resonant oscillation method.

Table 6 shows the evaluation results of the physical properties. TABLE 6Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 CEx. 9 Cured Cured Cured Cured CuredCured product product product product product product Tg(° C.) 172 175174 176 178 105 dielectric 2.80 2.81 2.77 2.81 2.77 3.21 constant (1GHz) dielectric 0.0122 0.0117 0.0113 0.0125 0.0123 0.0301 loss tangent(1 GHz)Ex. = Example, CEX = Comparative Example

Example 17

Synthesis of Bifunctional PPE Oligomer Compound

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) ofdi-n-butylamine and 400 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a solution obtained bydissolving 45.4 g (0.16 mol) of a bivalent phenol4,4′-(1-methylethylidene)bis(2,6-dimethylphenol) and 58.6 g (0.48 mol)of 2,6-dimehtylphenol in 800 g of methyl ethyl ketone was dropwise addedto the reactor over 120 minutes while carrying out bubbling with 2 L/minof air. After the completion of the addition, stirring was carried outfor 60 minutes while continuing the bubbling with 2 L/min of air. Adisodium dihydrogen ethylenediamine tetraacetate aqueous solution wasadded to the reaction solution to terminate the reaction. Then, washingwas carried out with 1N hydrochloric acid aqueous solution and thenwashing was carried out with pure water. The thus-obtained solution wasconcentrated by an evaporator and then dried under reduced pressure, toobtain 98.8 g of an oligomer compound. The oligomer compound had anumber average molecular weight of 845, a weight average molecularweight of 1,106 and a hydroxyl group equivalent of 451.

(Synthesis of Epoxy Compound)

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 49.6 g (hydroxyl group 0.11mol) of the above oligomer compound and 292 g of epichlorohydrin. Then,a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in30 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with pure water, and furthera filtration was carried out, to remove a generated salt and impurities.Excess epichlorohydrin was distilled off from the obtained solution, anddrying under reduced pressure was carried out, to obtain 53.6 g of anepoxy compound. According to the IR analysis of the obtained epoxycompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared, and according to the NMR analysis, a peak derived fromglycidyl ether appeared so that it was confirmed that all functionalgroups were changed. The epoxy compound had a number average molecularweight of 998, a weight average molecular weight of 1,277 and an epoxyequivalent of 565.

(Synthesis of Epoxy Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 26 g of the above epoxy compound, 3.3 g of an acrylic acid,20 g of carbitol acetate, 0.13 g of triphenylphosphine and 13 mg ofhydroquinone methyl ether. The mixture was heated up to 120° C., and itwas allowed to react with stirring. During the reaction, an acid valuewas measured, and the reaction was continued until the acid value became2 mgKOH/g. The stirring time at 120° C. was 5 hours. The reactionsolution was diluted with 40 g of methyl ethyl ketone. The dilutedreaction solution was dropwise added to methanol to obtain a precipitateagain. A solid was recovered by a filtration, and then drying underreduced pressure was carried out to obtain 26.4 g of an epoxy acrylatecompound. The epoxy acrylate compound had a number average molecularweight of 1,388 and a weight average molecular weight of 1,679.

(Synthesis of Acid-Modified Epoxy Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 11.3 g of the above epoxy acrylate compound, 7.4 g ofcarbitol acetate and 2.5 g of tetrahydrophthalic acid anhydride. Themixture was heated up to 80° C., and it was allowed to react withstirring. After 8 hours, according to IR measurement, a peak derivedfrom the acid anhydride disappeared, and therefore the reaction wasterminated to obtain an acid-modified epoxy acrylate compound. The acidvalue of the acid-modified epoxy acrylate compound was 71 mgKOH/g. Theacid-modified epoxy acrylate compound had a number average molecularweight of 1,697 and a weight average molecular weight of 2,036.

10 g of the epoxy acrylate compound was molten, degassed and molded at150° C. and then cured at 200° C. for 6 hours to obtain a cured product.

6 g of the epoxy acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface with a screen printing machine and thendried with an air dryer at 80° C. for 30 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at2,000 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was HB.

1 g of Darocur 1173 (supplied by Ciba Specialty Chemicals,photopolymerization initiator) was added to 10 g of the acid-modifiedepoxy acrylate compound to obtain a resin composition. The resincomposition was applied to a copper-clad laminate surface with a screenprinting machine and then dried with an air dryer at 80° C. for 30minutes, to obtain a coating. A pattern film was placed on the coating,and the coating was exposed at 2,000 mJ with a UV irradiation device(supplied by EYE GRAPHICS Co., Ltd.: UB0151, light source: metal halidelamp). After the exposure, development was carried out with 1% sodiumhydroxide aqueous solution. In this case, only non-exposed portions weredissolved in the sodium hydroxide aqueous solution, to obtain adevelopment pattern of a resin-cured product. A pencil mar strength (JISK5400) of the resin-cured product was HB.

Example 18

(Synthesis of Bifunctional PPE Oligomer Compound)

102.6 g of an oligomer compound was obtained in the same manner as inthe synthesis of bifunctional PPE oligomer compound in Example 17,except that 45.4 g (0.16 mol) of the bivalent phenol4,4′-(1-methylethylidene)bis(2,6-dimethylphenol) was replaced with 51.8g (0.16 mol) of a bivalent phenol4,4′-cyclohexylidenebis(2,6-dimehtylphenol). The oligomer compound had anumber average molecular weight of 877, a weight average molecularweight of 1,183 and a hydroxyl group equivalent of 477.

(Synthesis of Epoxy Compound)

54.1 g of an epoxy compound was obtained in the same manner as inExample 17, except that 49.6 g (hydroxyl group 0.11 mol) of the oligomercompound used in the synthesis of epoxy compound in Example 17 wasreplaced with 52.5 g (hydroxyl group 0.11 mol) of the oligomer compoundobtained above. According to the IR analysis of the obtained epoxycompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared and, according to the NMR analysis, a peak derived fromglycidyl ether appeared so that it was confirmed that all functionalgroups were changed. The epoxy compound had a number average molecularweight of 1,029, a weight average molecular weight of 1,301 and an epoxyequivalent of 576.

(Synthesis of Epoxy Acrylate Compound)

26.5 g of an epoxy acrylate compound was obtained in the same manner asin Example 17, except that 26 g of the epoxy compound used in thesynthesis of epoxy acrylate compound in Example 17 was replaced with26.5 g of the epoxy compound obtained above. The epoxy acrylate compoundhad a number average molecular weight of 1,411 and a weight averagemolecular weight of 1,721.

(Synthesis of Acid-Modified Epoxy Acrylate Compound)

An acid-modified epoxy acrylate compound was obtained in the same manneras in Example 17, except that 11.3 g of the epoxy acrylate compound and7.4 g of carbitol acetate used in the synthesis of acid-modified epoxyacrylate compound in Example 17 were replaced with 11.5 g of the epoxyacrylate compound obtained above and 7.5 g of carbitol acetaterespectively. The acid value of the acid-modified epoxy acrylatecompound was 69 mgKOH/g. The acid-modified epoxy acrylate compound had anumber average molecular weight of 1,733 and a weight average molecularweight of 2,094.

10 g of the epoxy acrylate compound was molten, degassed and molded at150° C. and then cured at 200° C. for 6 hours to obtain a cured product.

6 g of the epoxy acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface with a screen printing machine and thendried with an air dryer at 80° C. for 30 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at2,000 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was HB.

1 g of Darocur 1173 (supplied by Ciba Specialty Chemicals,photopolymerization initiator) was added to 10 g of the acid-modifiedepoxy acrylate compound to obtain a resin composition. The resincomposition was applied to a copper-clad laminate surface with a screenprinting machine and then dried with an air dryer at 80° C. for 30minutes, to obtain a coating. A pattern film was placed on the coating,and the coating was exposed at 2,000 mJ with a UV irradiation device(supplied by EYE GRAPHICS Co., Ltd.: UB0151, light source: metal halidelamp). After the exposure, development was carried out with 1% sodiumhydroxide aqueous solution. In this case, only non-exposed portions weredissolved in the sodium hydroxide aqueous solution, to obtain adevelopment pattern of a resin-cured product. A pencil mar strength (JISK5400) of the resin-cured product was HB.

Example 19

Synthesis of Bifunctional PPE Oligomer Compound

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) ofdi-n-butylamine and 400 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a solution obtained bydissolving 45.4 g (0.16 mol) of a bivalent phenol4,4′-methylidenebis(2,3,6-trimethylphenol) and 58.6 g (0.48 mol) of2,6-dimehtylphenol in 800 g of methyl ethyl ketone was dropwise added tothe reactor over 120 minutes while carrying out bubbling with 2 L/min ofair. After the completion of the addition, stirring was carried out for60 minutes while continuing the bubbling with 2 L/min of air. A disodiumdihydrogen ethylenediamine tetraacetate aqueous solution was added tothe reaction solution to terminate the reaction. Then, washing wascarried out with 1N hydrochloric acid aqueous solution and then washingwas carried out with pure water. The thus-obtained solution wasconcentrated by an evaporator and then dried under reduced pressure, toobtain 97.4 g of an oligomer compound. The oligomer compound had anumber average molecular weight of 852, a weight average molecularweight of 1,133 and a hydroxyl group equivalent of 460.

(Synthesis of Epoxy Compound)

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 50.6 g (hydroxyl group 0.11mol) of the above oligomer compound and 292 g of epichlorohydrin. Then,a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in30 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with pure water, and furthera filtration was carried out, to remove a generated salt and impurities.Excess epichlorohydrin was distilled off from the obtained solution, anddrying under reduced pressure was carried out, to obtain 53.8 g of anepoxy compound. According to the IR analysis of the obtained epoxycompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared, and according to the NMR analysis, a peak derived fromglycidyl ether appeared so that it was confirmed that all functionalgroups were changed. The epoxy compound had a number average molecularweight of 1,005, a weight average molecular weight of 1,275 and an epoxyequivalent of 566.

(Synthesis of Epoxy Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 26 g of the above epoxy compound, 3.3 g of an acrylic acid,20 g of carbitol acetate, 0.13 g of triphenylphosphine and 13 mg ofhydroquinone methyl ether. The mixture was heated up to 120° C., and itwas allowed to react with stirring. During the reaction, an acid valuewas measured, and the reaction was continued until the acid value became2 mgKOH/g. The stirring time at 120° C. was 5 hours. The reactionsolution was diluted with 40 g of methyl ethyl ketone. The dilutedreaction solution was dropwise added to methanol to obtain a precipitateagain. A solid was recovered by a filtration, and then drying underreduced pressure was carried out to obtain 26.7 g of an epoxy acrylatecompound. The epoxy acrylate compound had a number average molecularweight of 1,395 and a weight average molecular weight of 1,687.

(Synthesis of Acid-Modified Epoxy Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 11.4 g of the above epoxy acrylate compound, 7.5 g ofcarbitol acetate and 2.5 g of tetrahydrophthalic acid anhydride. Themixture was heated up to 80° C., and it was allowed to react withstirring. After 8 hours, according to IR measurement, a peak derivedfrom the acid anhydride disappeared, and therefore the reaction wasterminated to obtain an acid-modified epoxy acrylate compound. The acidvalue of the acid-modified epoxy acrylate compound was 68 mgKOH/g. Theacid-modified epoxy acrylate compound had a number average molecularweight of 1,704 and a weight average molecular weight of 2,044.

10 g of the epoxy acrylate compound was molten, degassed and molded at150° C. and then cured at 200° C. for 6 hours to obtain a cured product.

6 g of the epoxy acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface with a screen printing machine and thendried with an air dryer at 80° C. for 30 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at2,000 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was HB.

1 g of Darocur 1173 (supplied by Ciba Specialty Chemicals,photopolymerization initiator) was added to 10 g of the acid-modifiedepoxy acrylate compound to obtain a resin composition. The resincomposition was applied to a copper-clad laminate surface with a screenprinting machine and then dried with an air dryer at 80° C. for 30minutes, to obtain a coating. A pattern film was placed on the coating,and the coating was exposed at 2,000 mJ with a UV irradiation device(supplied by EYE GRAPHICS Co., Ltd.: UB0151, light source: metal halidelamp). After the exposure, development was carried out with 1% sodiumhydroxide aqueous solution. In this case, only non-exposed portions weredissolved in the sodium hydroxide aqueous solution, to obtain adevelopment pattern of a resin-cured product. A pencil mar strength (JISK5400) of the resin-cured product was HB.

Example 20

(Synthesis of Bifunctional PPE Oligomer Compound)

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) ofdi-n-butylamine and 400 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a solution obtained bydissolving 68.8 g (0.16 mol) of a bivalent phenol4,4′-[1,4-phenylenebis(1-methylethylidene)]bis(2,3,6-trime htylphenol)and 58.6 g (0.48 mol) of 2,6-dimehtylphenol in 800 g of methyl ethylketone was dropwise added to the reactor over 120 minutes while carryingout bubbling with 2 L/min of air. After the completion of the addition,stirring was carried out for 60 minutes while continuing the bubblingwith 2 L/min of air. A disodium dihydrogen ethylenediamine tetraacetateaqueous solution was added to the reaction solution to terminate thereaction. Then, washing was carried out with 1N hydrochloric acidaqueous solution and,then washing was carried out with pure water. Thethus-obtained solution was concentrated by an evaporator and then driedunder reduced pressure, to obtain 114.6 g of an oligomer compound. Theoligomer compound had a number average molecular weight of 934, a weightaverage molecular weight of 1,223 and a hydroxyl group equivalent of496.

(Synthesis of Epoxy Compound)

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 54.6 g (hydroxyl group 0.11mol) of the above oligomer compound and 292 g of epichlorohydrin. Then,a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in30 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with pure water, and furthera filtration was carried out, to remove a generated salt and impurities.Excess epichlorohydrin was distilled off from the obtained solution, anddrying under reduced pressure was carried out, to obtain 56.9 g of anepoxy compound. According to the IR analysis of the obtained epoxycompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared, and according to the NMR analysis, a peak derived fromglycidyl ether appeared so that it was confirmed that all functionalgroups were changed. The epoxy compound had a number average molecularweight of 1,092, a weight average molecular weight of 1,408 and an epoxyequivalent of 612.

(Synthesis of Epoxy Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 28.1 g of the above epoxy compound, 3.3 g of an acrylicacid, 20 g of carbitol acetate, 0.13 g of triphenylphosphine and 13 mgof hydroquinone methyl ether. The mixture was heated up to 120° C., andit was allowed to react with stirring. During the reaction, an acidvalue was measured, and the reaction was continued until the acid valuebecame 2 mgKOH/g. The stirring time at 120° C. was 5 hours. The reactionsolution was diluted with 40 g of methyl ethyl ketone. The dilutedreaction solution was dropwise added to methanol to obtain a precipitateagain. A solid was recovered by a filtration and then drying underreduced pressure was carried out to obtain 28.3 g of an epoxy acrylatecompound. The epoxy acrylate compound had a number average molecularweight of 1,497 and a weight average molecular weight of 1,841.

(Synthesis of Acid-Modified Epoxy Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 12.1 g of the above epoxy acrylate compound, 7.9 g ofcarbitol acetate and 2.5 g of tetrahydrophthalic acid anhydride. Themixture was heated up to 80° C., and it was allowed to react withstirring. After 8 hours, according to IR measurement, a peak derivedfrom the acid anhydride disappeared, and therefore the reaction wasterminated to obtain an acid-modified epoxy acrylate compound. The acidvalue of the acid-modified epoxy acrylate compound was 65 mgKOH/g. Theacid-modified epoxy acrylate compound had a number average molecularweight of 1,810 and a weight average molecular weight of 2,225.

10 g of the epoxy acrylate compound was molten, degassed and molded at150° C. and then cured at 200° C. for 6 hours to obtain a cured product.

6 g of the epoxy acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface with a screen printing machine and thendried with an air dryer at 80° C. for 30 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at2,000 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was HB.

1 g of Darocur 1173 (supplied by Ciba Specialty Chemicals,photopolymerization initiator) was added to 10 g of the acid-modifiedepoxy acrylate compound to obtain a resin composition. The resincomposition was applied to a copper-clad laminate surface with a screenprinting machine and then dried with an air dryer at 80° C. for 30minutes, to obtain a coating. A pattern film was placed on the coating,and the coating was exposed at 2,000 mJ with a UV irradiation device(supplied by EYE GRAPHICS Co., Ltd.: UB0151, light source: metal halidelamp). After the exposure, development was carried out with 1% sodiumhydroxide aqueous solution. In this case, only non-exposed portions weredissolved in the sodium hydroxide aqueous solution, to obtain adevelopment pattern of a resin-cured product. A pencil mar strength (JISK5400) of the resin-cured product was HB.

Example 21

(Synthesis of Bifunctional PPE Oligomer Compound)

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) ofdi-n-butylamine and 400 g of methyl ethyl ketone. The components werestirred at a reaction temperature of 40° C., and a solution obtained bydissolving 41.0 g (0.16 mol) of a bivalent phenol4,4′-methylenebis(2,6-dimethylphenol) and 58.6 g (0.48 mol) of2,6-dimehtylphenol in 800 g of methyl ethyl ketone was dropwise added tothe reactor over 120 minutes while carrying out bubbling with 2 L/min ofair. After the completion of the addition, stirring was carried out for60 minutes while continuing the bubbling with 2 L/min of air. A disodiumdihydrogen ethylenediamine tetraacetate aqueous solution was added tothe reaction solution to terminate the reaction. Then, washing wascarried out with 1N hydrochloric acid aqueous solution and then washingwas carried out with pure water. The thus-obtained solution wasconcentrated by an evaporator and then dried under reduced pressure, toobtain 94.6 g of an oligomer compound. The oligomer compound had anumber average molecular weight of 801, a weight average molecularweight of 1,081 and a hydroxyl group equivalent of 455.

(Synthesis of Epoxy Compound)

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas heated up to 100° C. and charged with 50.1 g (hydroxyl group 0.11mol) of the above oligomer compound and 292 g of epichlorohydrin. Then,a solution obtained by dissolving 8.6 g (0.13 mol) of sodium ethoxide in30 g of ethanol was dropwise added from the dropping funnel over 60minutes. After the completion of the addition, stirring was carried outfor 5 hours. Then, washing was carried out with pure water, and furthera filtration was carried out, to remove a generated salt and impurities.Excess epichlorohydrin was distilled off from the obtained solution, anddrying under reduced pressure was carried out, to obtain 50.2 g of anepoxy compound. According to the IR analysis of the obtained epoxycompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared, and according to the NMR analysis, a peak derived fromglycidyl ether appeared so that it was confirmed that all functionalgroups were changed. The epoxy compound had a number average molecularweight of 956, a weight average molecular weight of 1,204 and an epoxyequivalent of 545.

(Synthesis of Epoxy Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a ref lux tube wascharged with 25.1 g of the above epoxy compound, 3.3 g of an acrylicacid, 20 g of carbitol acetate, 0.13 g of triphenylphosphine and 13 mgof hydroquinone methyl ether. The mixture was heated up to 120° C., andit was allowed to react with stirring. During the reaction, an acidvalue was measured, and the reaction was continued until the acid valuebecame 2 mgKOH/g. The stirring time at 120° C. was 5 hours. The reactionsolution was diluted with 40 g of methyl ethyl ketone. The dilutedreaction solution was dropwise added to methanol to obtain a precipitateagain. A solid was recovered by a filtration, and then drying underreduced pressure was carried out to obtain 25.4 g of an epoxy acrylatecompound. The epoxy acrylate compound had a number average molecularweight of 1,359 and a weight average molecular weight of 1,657.

(Synthesis of Acid-Modified Epoxy Acrylate Compound)

A reactor equipped with a stirrer, a thermometer and a reflux tube wascharged with 11.0 g of the above epoxy acrylate compound, 7.3 g ofcarbitol acetate and 2.5 g of tetrahydrophthalic acid anhydride. Themixture was heated up to 80° C., and it was allowed to react withstirring. After 8 hours, according to IR measurement, a peak derivedfrom the acid anhydride disappeared, and therefore the reaction wasterminated to obtain an acid-modified epoxy acrylate compound. The acidvalue of the acid-modified epoxy acrylate compound was 71 mgKOH/g. Theacid-modified epoxy acrylate compound had a number average molecularweight of 1, 681 and a weight average molecular weight of 2,101.

10 g of the epoxy acrylate compound was molten, degassed and molded at150° C. and then cured at 200° C. for 6 hours to obtain a cured product.

6 g of the epoxy acrylate compound was dissolved in 4 g of carbitolacetate, and 0.6 g of Darocur 1173 (supplied by Ciba SpecialtyChemicals, photopolymerization initiator) was added to the solution toobtain a resin composition. The resin composition was applied to acopper-clad laminate surface with a screen printing machine and thendried with an air dryer at 80° C. for 30 minutes, to obtain a coating. Apattern film was placed on the coating, and the coating was exposed at2,000 mJ with a UV irradiation device (supplied by EYE GRAPHICS Co.,Ltd.: UB0151, light source: metal halide lamp). After the exposure,development was carried out with methyl ethyl ketone. In this case, onlynon-exposed portions were dissolved in the methyl ethyl ketone, toobtain a development pattern of a resin-cured product. A pencil marstrength (JIS K5400) of the resin-cured product was HB.

1 g of Darocur 1173 (supplied by Ciba Specialty Chemicals,photopolymerization initiator) was added to 10 g of the acid-modifiedepoxy acrylate compound to obtain a resin composition. The resincomposition was applied to a copper-clad laminate surface with a screenprinting machine and then dried with an air dryer at 80° C. for 30minutes, to obtain a coating. A pattern film was placed on the coating,and the coating was exposed at 2,000 mJ with a UV irradiation device(supplied by EYE GRAPHICS Co., Ltd.: UB0151, light source: metal halidelamp). After the exposure, development was carried out with 1% sodiumhydroxide aqueous solution. In this case, only non-exposed portions weredissolved in the sodium hydroxide aqueous solution, to obtain adevelopment pattern of a resin-cured product. A pencil mar strength (JISK5400) of the resin-cured product was HB.

Comparative Example 10

38 g of tetramethylbisphenoldiglycidyl ether (YX4000: supplied by JapanEpoxy Resins Co., Ltd: epoxy equivalent 190) and 14.4 g of acrylic acidwere dissolved at 60° C. Then, 0.19 g of triphenylphosphine and 19 mg ofhydroquinone methyl ether were added to the mixture. The resultantmixture was heated up to 100° C., and the mixture was stirred for 10hours. During the reaction, an acid value was measured. After the acidvalue became 2 mgKOH/g, the mixture was cooled down to 60° C. to obtaina resin. The resin was a viscous liquid at 60° C.

Comparative Example 11

10 g of the same resin as that obtained in Comparative Example 10 wasmolten, degassed and molded at 120° C. and then cured at 200° C. for 6hours to obtain a cured product.

Comparative Example 12

10 g of bisphenol A type epoxy acrylate (SP1509, supplied by SHOWAHIGHPOLYMER CO., LTD) was degassed and molded at 120° C. and then curedat 200° C. for 6 hours to obtain a cured product.

Comparative Example 13

10 g of novolak type epoxy acrylate (SP4010, supplied by SHOWAHIGHPOLYMER CO., LTD) was degassed and molded at 120° C. and then curedat 200° C. for 6 hours to obtain a cured product.

The cured products obtained in Examples 17-21 and Comparative Example11-13 were evaluated for properties by the following methods.

Glass transition temperature (Tg): Obtained by dynamic viscoelasticitymeasurement (DMA). Measurements were carried out at an oscillationfrequency of 10 Hz.

Dielectric constant and dielectric loss tangent: Obtained according to acavity resonant oscillation method.

Table 7 shows the evaluation results of the above properties. TABLE 7CEx. CEx. CEx. Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 11 12 13 Cured CuredCured Cured Cured Cured Cured Cured product product product productproduct product product product Tg(° C.) 182 185 185 188 191 165 140 142dielectric 2.81 2.83 2.79 2.82 2.77 3.12 3.31 3.10 constant (1 GHz)dielectric 0.025 0.022 0.021 0.021 0.023 0.036 0.052 0.032 loss tangent(1 GHz)Ex. = Example, CEX = Comparative Example

Example 22

(Production Process of Bifunctional PPE Oligomer Compound)

A longitudinally long reactor having a volume of 2 liters and equippedwith a stirrer, a thermometer, an air-introducing tube and baffleplateswas charged with 1.3 g (0.013 mol) of CuCl, 79.5 g (0.62 mol) ofdi-n-butylamine and 400 g of toluene. The components were stirred at areaction temperature of 40° C. A mixed solution (bivalent phenol of theformula (7): monovalent phenol of the formula (8) in a molar ratio=1:4)obtained by dissolving 48.6 g (0.15 mol) of a bivalent phenol4,4′-cyclohexylidenebis(2,6-dimehtylphenol) and 73.3 g (0.60 mol) of2,6-dimehtylphenol in 400 g of methyl ethyl ketone was dropwise added tothe reactor over 120 minutes while carrying out bubbling with 2 L/min ofair. After the completion of the addition, stirring was carried out for60 minutes while continuing the bubbling with 2 L/min of air. A disodiumdihydrogen ethylenediamine tetraacetate aqueous solution was added tothe reaction solution to terminate the reaction. Then, washing wascarried out with 1N hydrochloric acid aqueous solution and then washingwas carried out with pure water. The thus-obtained solution wasconcentrated by an evaporator and then dried under reduced pressure, toobtain 120.2 g of an oligomer compound. The oligomer compound had anumber average molecular weight of 1,100, a weight average molecularweight of 1,530 and a hydroxyl group equivalent of 545.

(Production Process of Cyanate Compound)

A reactor equipped with a stirrer, a thermometer and a dropping funnelwas cooled down to −10° C. 200 ml of a methylene chloride solutioncontaining cyanogen chloride (0.144 mol) was placed in the reactor.Then, a solution obtained by dissolving 52.8 g (hydroxyl group 0.096mol) of the above oligomer compound and 14.6 g (0.144 mol) oftriethylamine in 250 g of methyl ethyl ketone, was dropwise added fromthe dropping funnel over 60 minutes so as to maintain the temperature ofthe reaction solution at 10° C. or less. After the completion of theaddition, stirring was carried out for 60 minutes. Then, washing wascarried out with 0.1N hydrochloric acid aqueous solution, then washingwas carried out with pure water, and further a filtration was carriedout, to remove a generated salt and impurities. The methylene chlorideand the methyl ethyl ketone were evaporated from the obtained solutionand drying under reduced pressure was carried out, to obtain 53.3 g of acyanate compound. According to the IR analysis of the obtained cyanatecompound, the absorption peak (3,600 cm-1) of a phenolic hydroxyl groupdisappeared and the absorption peak (2,250 cm-1) derived from a cyanategroup appeared so that it was confirmed that all functional groups werechanged.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 237° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.70 and its dielectric loss tangentwas 0.0068.

Example 23

(Production Process of Bifunctional PPE Oligomer Compound)

122.5 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenolsof the formula (8) in a molar ratio=1:4) obtained by dissolving 48.6 g(0.15 mol) of a bivalent phenol4,4′-cyclohexylidenebis(2,6-dimehtylphenol), 55.0 g (0.45 mol) of2,6-dimehtylphenol and 20.4 g (0.15 mol) of 2,3,6-trimethylphenol in 400g of methyl ethyl ketone and 400 g of tetrahydrofuran. The oligomercompound had a number average molecular weight of 1,080, a weightaverage molecular weight of 1,520 and a hydroxyl group equivalent of545.

(Production Process of Cyanate Compound)

53.5 g of a cyanate compound was obtained in the same manner as inExample 22, except that the oligomer-compound-dissolved solution used inthe production process of cyanate compound in Example 22 was replacedwith a solution obtained by dissolving 52.3 g (hydroxyl group 0.096 mol)of the above oligomer compound and 14.6 g (0.144 mol) of triethylaminein 250 g of methyl ethyl ketone. According to the IR analysis of theobtained cyanate compound, the absorption peak (3,600 cm-1) of aphenolic hydroxyl group disappeared and the absorption peak (2,250 cm-1)derived from a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 243° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.69 and its dielectric loss tangentwas 0.0055.

Example 24

(Production Process of Bifunctional PPE Oligomer Compound)

118.2 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenolsof the formula (8) in a molar ratio=1:4) obtained by dissolving 46.5 g(0.15 mol) of a bivalent phenol4,4′-cyclopentylidenebis(2,6-dimehtylphenol) and73.3 g (0.60 mol) of2,6-dimehtylphenol in 400 g of methyl ethyl ketone and 400 g oftetrahydrofuran. The oligomer compound had a number average molecularweight of 1,070, a weight average molecular weight of 1,500 and ahydroxyl group equivalent of 540.

(Production Process of Cyanate Compound)

52.2 g of a cyanate compound was obtained in the same manner as inExample 22, except that the oligomer-compound-dissolved solution used inthe production process of cyanate compound in Example 22 was replacedwith a solution obtained by dissolving 51.8 g (hydroxyl group 0.096 mol)of the above oligomer compound and 14.6 g (0.144 mol) of triethylaminein 250 g of methyl ethyl ketone. According to the IR analysis of theobtained cyanate compound, the absorption peak (3,600 cm-1) of aphenolic hydroxyl group disappeared and the absorption peak (2,250 cm-1)derived from a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 236° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.73 and its dielectric loss tangentwas 0.0062.

Example 25

(Production Process of Bifunctional PPE Oligomer Compound)

135.3 g of an oligomer compound was obtained in the same manner as inthe production process of bifunctional PPE oligomer compound in Example22, except that 2.7 g (0.012 mol) of CuBr₂, 70.7 g (0.55 mol) ofdi-n-butylamine and 600 g of methyl ethyl ketone were placed in the samereactor as that used in Example 22 and stirred at a reaction temperatureof 40° C. and that a mixed solution (bivalent phenol of the formula (7):monovalent phenol of the formula (8) in a molar ratio=1:2) obtained bydissolving 85.3 g (0.21 mol) of a bivalent phenol4,4′-(9H-fluorene-9-ylidene)bis(2,6-dimehtylphenol) and 51.3 g (0.41mol) of 2,6-dimehtylphenol in 600 g of methyl ethyl ketone and 400 g oftetrahydrofuran was bubbled with 2 L/min of air. The oligomer compoundhad a number average molecular weight of 650, a weight average molecularweight of 810 and a hydroxyl group equivalent of 320.

(Production Process of Cyanate Compound)

31.2 g of a cyanate compound was obtained in the same manner as inExample 22, except that the oligomer-compound-dissolved solution used inthe production process of cyanate compound in Example 22 was replacedwith a solution obtained by dissolving 30.7 g (hydroxyl group 0.096 mol)of the above oligomer compound and 14.6 g (0.144 mol) of triethylaminein 250 g of methyl ethyl ketone. According to the IR analysis of theobtained cyanate compound, the absorption peak (3,600 cm-1) of aphenolic hydroxyl group disappeared and the absorption peak (2,250 cm-1)derived from a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 273° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.74 and its dielectric loss tangentwas 0.0068.

Comparative Example 14

(Production Process of Bifunctional PPE Oligomer Compound)

113.1 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenol ofthe formula (8) in a molar ratio=1:4) obtained by dissolving 42.6 g(0.15 mol) of a bivalent phenol4,4′-(1-methylethylidene)bis(2,6-dimehtylphenol) and 73.3 g (0.60 mol)of 2,6-dimehtylphenol in 400 g of methyl ethyl ketone. The oligomercompound had a number average molecular weight of 1,030, a weightaverage molecular weight of 1,460 and a hydroxyl group equivalent of540.

(Production Process of Cyanate Compound)

53.2 g of a cyanate compound was obtained in the same manner as inExample 22, except that the oligomer-compound-dissolved solution used inthe production process of cyanate compound in Example 22 was replacedwith a solution obtained by dissolving 51.8 g (hydroxyl group 0.096 mol)of the above oligomer compound and 14.6 g (0.144 mol) of triethylaminein 250 g of methyl ethyl ketone. According to the IR analysis of theobtained cyanate compound, the absorption peak (3,600 cm-1) of aphenolic hydroxyl group disappeared and the absorption peak (2,250 cm-1)derived from a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 228° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.83 and its dielectric loss tangentwas 0.0079.

Table 8 shows the above results. TABLE 8 Ex. 22 Ex. 23 Ex. 24 Ex. 25CEx. 14 dielectric 2.7 2.69 2.73 2.74 2.83 constant (1 GHz) dielectric0.0068 0.0055 0.0062 0.0068 0.0079 loss tangent (1 GHz) Tg (DMA)/ 237243 236 273 228 (° C.)Ex. = Example, CEX = Comparative Example

Example 26

(Production Process of Bifunctional PPE Oligomer Compound)

113.2 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenol ofthe formula (8) in a molar ratio=1:4) obtained by dissolving 42.6 g(0.15 mol) of a bivalent phenol 4,4′-methylenebis[2,3,6-trimehtylphenol]and 73.3 g (0.60 mol) of 2,6-dimehtylphenol in 400 g of methyl ethylketone and 400 g of tetrahydrofuran. The oligomer compound had a numberaverage molecular weight of 1,050, a weight average molecular weight of1,490 and a hydroxyl group equivalent of 550.

(Production Process of Cyanate Compound)

53.0 g of a cyanate compound was obtained in the same manner as inExample 22, except that the dissolved solution used in Example 22 wasreplaced with a solution obtained by dissolving 52.8 g (hydroxyl group0.096 mol) of the above oligomer compound and 14.6 g (0.144 mol) oftriethylamine in 250 g of methyl ethyl ketone. According to the IRanalysis of the obtained cyanate compound, the absorption peak (3,600cm-1) of a phenolic hydroxyl group disappeared and the absorption peak(2,250 cm-1) derived from a cyanate group appeared so that it wasconfirmed that all functional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 235° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.72 and its dielectric loss tangentwas 0.0063.

Example 27

(Production Process of Bifunctional PPE Oligomer Compound)

116.5 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenolsof the formula (8) in a molar ratio=1:4) obtained by dissolving 42.6 g(0.15 mol) of a bivalent phenol4,4′-methylenebis[2,3,6-trimehtylphenol], 55.0 g (0.45 mol) of2,6-dimehtylphenol and 20.4 g (0.15 mol) of 2,3,6-trimethylphenol in 400g of methyl ethyl ketone and 400 g of tetrahydrofuran. The oligomercompound had a number average molecular weight of 1,020, a weightaverage molecular weight of 1,450 and a hydroxyl group equivalent of540.

(Production Process of Cyanate Compound)

53.3 g of a cyanate compound was obtained in the same manner as inExample 22, except that the dissolved solution used in the productionprocess of cyanate compound in Example 22 was replaced with a solutionobtained by dissolving 51.8 g (hydroxyl group 0.096 mol) of the aboveoligomer compound and 14.6 g (0.144 mol) of triethylamine in 250 g ofmethyl ethyl ketone. According to the IR analysis of the obtainedcyanate compound, the absorption peak (3,600 cm-1) of a phenolichydroxyl group disappeared and the absorption peak (2,250 cm-1) derivedfrom a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 245° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.70 and its dielectric loss tangentwas 0.0055.

Example 28

(Production Process of Bifunctional PPE Oligomer Compound)

128.2 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenol ofthe formula (8) in a molar ratio=1:4) obtained by dissolving 56.1 g(0.15 mol) of a bivalent phenol4,4′-(1,4-phenylenebismethylene)bis(2,3,6-trimethylphenol) and 73.3 g(0.60 mol) of 2,6-dimehtylphenol in 400 g of methyl ethyl ketone. Theoligomer compound had a number average molecular weight of 1,120, aweight average molecular weight of 1,580 and a hydroxyl group equivalentof 560.

(Production Process of Cyanate Compound)

54.2 g of a cyanate compound was obtained in the same manner as inExample 22, except that the dissolved solution used in the productionprocess of cyanate compound in Example 22 was replaced with a solutionobtained by dissolving 53.8 g (hydroxyl group 0.096 mol) of the aboveoligomer compound and 14.6 g (0.144 mol) of triethylamine in 250 g ofmethyl ethyl ketone. According to the IR analysis of the obtainedcyanate compound, the absorption peak (3,600 cm-1) of a phenolichydroxyl group disappeared and the absorption peak (2,250 cm-1) derivedfrom a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 241° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.72 and its dielectric loss tangentwas 0.0065.

Example 29

(Production Process of Bifunctional PPE Oligomer Compound)

114.8 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenol ofthe formula (8) in a molar ratio=1:8) obtained by dissolving 33.1 g(0.077 mol) of a bivalent phenol4,4′-[1,4-phenylenebis(1-methylethylidene)]bis(2,3,6-trime htylphenol)and 75.6 g (0.62 mol) of 2,6-dimehtylphenol and 20.4 g (0.15 mol) of2,3,6-trimethylphenol in 600 g of methanol. The oligomer compound had anumber average molecular weight of 1,600, a weight average molecularweight of 2,280 and a hydroxyl group equivalent of 780.

(Production Process of Cyanate Compound)

75.3 g of a cyanate compound was obtained in the same manner as inExample 22, except that the dissolved solution used in the productionprocess of cyanate compound in Example 22 was replaced with a solutionobtained by dissolving 74.9 g (hydroxyl group 0.096 mol) of the aboveoligomer compound and 14.6 g (0.144 mol) of triethylamine in 250 g ofmethyl ethyl ketone. According to the IR analysis of the obtainedcyanate compound, the absorption peak (3,600 cm-1) of a phenolichydroxyl group disappeared and the absorption peak (2, 250 cm-1) derivedfrom a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 234° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.74 and its dielectric loss tangentwas 0.0055.

Comparative Example 15

(Production Process of Bifunctional PPE Oligomer Compound)

113.1 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenol ofthe formula (8) in a molar ratio=1:4) obtained by dissolving 42.6 g(0.15 mol) of a bivalent phenol4,4′-(1-methylethylidene)bis(2,6-dimehtylphenol) and 73.3 g (0.60 mol)of 2,6-dimehtylphenol in 400 g of methyl ethyl ketone. The oligomercompound had a number average molecular weight of 1,030, a weightaverage molecular weight of 1,460 and a hydroxyl group equivalent of540.

(Production Process of Cyanate Compound)

53.2 g of a cyanate compound was obtained in the same manner as inExample 22, except that the dissolved solution used in the productionprocess of cyanate compound in Example 22 was replaced with a solutionobtained by dissolving 51.8 g (hydroxyl group 0.096 mol) of the aboveoligomer compound and 14.6 g (0.144 mol) of triethylamine in 250 g ofmethyl ethyl ketone. According to the IR analysis of the obtainedcyanate compound, the absorption peak (3,600 cm-1) of a phenolichydroxyl group disappeared and the absorption peak (2,250 cm-1) derivedfrom a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

0.1 part of tin octylate was added to 100 parts of the thus-obtainedcyanate compound. The mixture was molten, degassed and molded at 160° C.and then cured at 230° C. for 3 hours, to obtain a cured product. Thecured product had a glass transition temperature of 228° C. according tothe measurement of dynamic viscoelasticity (DMA). Further, itsdielectric constant at 1 GHz was 2.83 and its dielectric loss tangentwas 0.0079.

Table 9 shows the above results. TABLE 9 Ex. 26 Ex. 27 Ex. 28 Ex. 29CEx. 15 dielectric 2.72 2.7 2.72 2.74 2.83 constant (1 GHz) dielectric0.0063 0.0055 0.0065 0.0055 0.0079 loss tangent (1 GHz) Tg (DMA)/ 235245 241 234 228 (° C.)Ex. = Example, CEX = Comparative Example

Example 30

Production Process of Cyanate Compound

(Production Process of Bifunctional PPE Oligomer Compound)

113.2 g of an oligomer compound was obtained in the same manner as inExample 22, except that the mixed solution used in the synthesis ofbifunctional PPE oligomer compound in Example 22 was replaced with amixed solution (bivalent phenol of the formula (7): monovalent phenol ofthe formula (8) in a molar ratio=1:4) obtained by dissolving 42.6 g(0.15 mol) of a bivalent phenol 4,4′-methylenebis[2,3,6-trimehtylphenol]and 73.3 g (0.60 mol) of 2,6-dimehtylphenol in 400 g of methyl ethylketone and 400 g of tetrahydrofuran. The oligomer compound had a numberaverage molecular weight of 1, 050, a weight average molecular weight of1,490 and a hydroxyl group equivalent of 550.

(Production Process of Cyanate Compound)

53.0 g of a cyanate compound was obtained in the same manner as inExample 22, except that the dissolved solution used in the productionprocess of cyanate compound in Example 22 was replaced with a solutionof 52.8 g (hydroxyl group 0.096 mol) of the above oligomer compound in250 g of methyl ethyl ketone. According to the IR analysis of theobtained cyanate compound, the absorption peak (3,600 cm-1) of aphenolic hydroxyl group disappeared and the absorption peak (2,250 cm-1)derived from a cyanate group appeared so that it was confirmed that allfunctional groups were changed.

30 parts of the above bifunctional cyanate compound, 30 parts ofbisphenol A type cyanate prepolymer, 20 parts of tetrabromobisphenol Aepoxy (supplied by Dainippon Ink And Chemicals, Incorporated, tradename: EPICLON-153), 20 parts of bisphenol A epoxy (supplied by DowChemical Japan Ltd. Trade name: DER-331L) and 0.04 part of ironacetylacetonate were dissolved in methyl ethyl ketone, to prepare avarnish having a resin content of 60%. A glass cloth (NE glass product:trade name WEX983, supplied by Nitto Boseki Co., Ltd.) was impregnatedwith the above varnish, and then it was treated with a hot-air dryer, toobtain B-stage prepreg. Eight sheets of the prepreg and a copper foil(thickness: 18 μm, supplied by Mitsui Mining & smelting Co., Ltd., tradename: 3EC-3) were laminated and these materials were hot-pressed at 200°C. in vacuum for 2 hours to obtain a 0.8 mm-thick copper-clad laminate.Table 11 shows the physical properties of the copper-clad laminate.

Comparative Example 16, 17

Copper-clad laminates were obtained in the same manner as in Example 30except that thermosetting resins were mixed in amount ratios shown inTable 10. In Comparative Example 16, toluene was used as a solvent,since an ingredient was insoluble in methyl ethyl ketone. TABLE 10 Ex.30 CEx. 16 CEx. 17 Bifunctional 30 — — OPE-2CN General-purpose PPE — 30— polymer Bisphenol A type 30 30 30 cyanate prepolymer 4,4′dimethyl —diphenylmethane Tetrabromobisphenol 20 20 20 A epoxy Bisphenol A epoxy20 20 10 Phenol novolak type — — 40 epoxy iron 0.04 0.04 0.04acetylacetonateEx. = Example,CEx. = Comparative Example

General-purpose PPE polymer: supplied by Mitsubishi Gas Chemical Co.,Inc., number average molecular weight: 24,000.

Bisphenol A type cyanate prepolymer: prepolymer of2,2-bis(4-cyanatophenyl)propane.

Tetrabromobisphenol A epoxy: EPICLON-153, supplied by Dainippon Ink AndChemicals, Incorporated.

Bisphenol A epoxy: DER-331L, supplied by Dow Chemical Japan Ltd.

Phenol novolak type epoxy: EPPN-201, supplied by Nippon Kayaku Co., Ltd.TABLE 11 Ex. 30 CEx. 16 CEx. 17 Grass transition 206° C. 202° C. 190° C.temperature (DMA method) Dielectric 3.5 3.5 4.0 constant(1 GHz)Dielectric loss tangent 0.0049 0.0046 0.014 (1 GHz) Copper-foil peeling1.2 1.2 0.9 strength (kN/m) Moldability ◯ X ◯ Heat resistance againstsoldering after moisture absorption (number of swelling/number of testedspecimens) 1 hour treatment 0/3 2/3 0/3 2 hours treatment 0/3 3/3 0/3 3hours treatment 0/3 3/3 1/3 Bending strength (MPa) 479 368 498 Bendingmodulus (MPa) 17,600 17,200 19,200 Deflection in bending (%) 2.9 2.4 2.8Ex. = Example,CEx. = Comparative Example

In Examples and Comparative Examples, measurements were carried out bythe following devices and methods.

-   -   Grass transition temperature (Tg): Obtained by a loss tangent        (tan δ) peak of a dynamic viscoelasticity measurement.    -   Dielectric constant and dielectric loss tangent: Measured        according to a cavity resonant oscillation method.    -   Copper foil peeling strength: Peeling strength of a copper foil        having a width of 10 mm in a 90-degree direction was measured        according to JIS C6481.    -   Moldability: Determined depending upon whether or not an        internal layer pattern of a 70 μm-thick copper foil could be        embedded without voids.    -   Heat resistance against soldering after moisture absorption: A        sample was prepared by removing the entire copper foil, the        sample was treated for absorption under PCT conditions at        121° C. at 0.2 MPa for 1 to 3 hours and then the sample was        immersed in a solder bath at 260° C. for 30 seconds. The sample        was visually observed for the occurrence of a delamination        (swelling).    -   Mechanical properties: Head speed: 1.0 mm/min, distance between        supports: 20 mm, measured at room temperature.

1-4. (cancel)
 5. A sealing epoxy resin composition containing asingredients an epoxy resin, a curing agent, an inorganic filler and apolyphenylene ether oligomer compound having a number average molecularweight of 700 to 3,000 and having an epoxy group at each terminal,represented by the formula (9),

wherein —(O—X—O)—, —(Y—O)—, Z, A and i are as defined in the formula(1), each of a and b is 0 or an integer of 1 to 20, provided that atleast either a or b is not 0, each of c and d is 0 or an integer of 1 to20, provided that at least either c or d is not 0, and j is 0 or aninteger of 1 to
 5. 6. A sealing epoxy resin composition according toclaim 5, wherein, in the polyphenylene ether oligomer compound having anepoxy group at each terminal, at least R₁, R₂, R₇ and R₈ in the formula(2) representing —(O—X—O)— are a methyl group, and —(Y—O)— has anarrangement structure of the formula (4) or the formula (5) or a randomarrangement structure of the formula (4) and the formula (5).
 7. Asealing epoxy resin composition according to claim 5, wherein thecontent of the polyphenylene ether oligomer compound having an epoxygroup at each terminal is 1 to 60% by weight based on the total amountof the epoxy resin, the curing agent and the polyphenylene etheroligomer compound having an epoxy group at each terminal.
 8. A sealingepoxy resin composition according to claim 5, wherein the content of theinorganic filler is 15 to 95% by weight based on the total amount of theepoxy resin, the curing agent, the inorganic filler and thepolyphenylene ether oligomer compound having an epoxy group at eachterminal.
 9. An epoxy resin composition for laminates, containing apolyphenylene ether oligomer epoxy compound having a number averagemolecular weight of 700 to 3,000 and having an epoxy group at eachterminal, represented by the formula (9) recited in claim 5, and acuring agent as ingredients.
 10. An epoxy resin composition forlaminates according to claim 9, which further contains a cyanate esterresin.
 11. An epoxy resin composition for laminates according to claim9, wherein in the polyphenylene ether oligomer epoxy compound having anepoxy group at each terminal represented by the formula (9), at leastR₁, R₂, R₇ and R₈ in the formula (2) representing —(O—X—O)— are a methylgroup and —(Y—O)— has an arrangement structure of the formula (4)recited in claim 4 or the formula (5) recited in claim 4 or a randomarrangement structure of the formula (4) and the formula (5). 12.Prepreg obtained from the epoxy resin composition recited in claim 9.13. A laminate obtained from the epoxy resin composition recited inclaim
 9. 14. A printed wiring board obtained from the epoxy resincomposition recited in claim
 9. 15-30. (Cancel)